JP2003252932A - Acrylic acid ester copolymer rubber and method producing the same, rubber composition, oil and weather resistant rubber composition and oil and weather resistant rubber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic acid ester copolymer rubber which is free from a halogen, can provide a rubber product with excellent fuel oil resistance and tensile strength, and can be crosslinked by sulfur or an organic peroxide; a method for producing the same; a rubber composition; an oil and weather resistant rubber composition; and an oil and weather resistant rubber. <P>SOLUTION: The acrylic acid ester copolymer rubber comprises a constituent unit derived from at least one monomer selected from an alkyl acrylate and an alkoxyalkyl acrylate at 40-91.9% by mass, a constituent unit derived from an unsaturated nitrile monomer at 8-40% by mass, and a constituent unit derived from at least one monomer selected from a non-conjugated cyclic polyene and a specific structure of a compound at 0.1-20% by mass (to sum up to 100% by mass), wherein the rubber has a Mooney viscosity [ML<SB>1+4</SB>(100°C)] of 10-200. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acrylic acid ester copolymer rubber, a method for producing the same, a rubber composition containing the same, an oil weatherproof rubber composition and an oil weatherproof rubber, and more specifically to a fuel resistant rubber composition. Acrylic ester-based copolymer rubber that gives a rubber product having excellent oiliness and also excellent tensile strength and is crosslinkable with sulfur and / or organic peroxide, and a method for producing the same, and a rubber composition and an oil-resistant and weather-resistant rubber composition And oil- and weather-resistant rubber.

[0002]

2. Description of the Related Art Conventionally, unsaturated nitrile / conjugated diene rubber has been known as a rubber having excellent oil resistance. However, this rubber alone was not excellent in weather resistance, particularly ozone resistance, because it has a double bond in the main chain. In order to improve this weather resistance, unsaturated nitrile / conjugated diene rubber, rubber containing unsaturated nitrile / conjugated diene rubber and polyvinyl chloride (Patent Document 1, etc.), unsaturated nitrile / conjugated diene rubber Rubber containing chlorinated polyethylene (Patent Document 2, etc.), further, acrylic rubber and ethylene-α-
Blends with olefin-based copolymers (Patent Document 3, Patent Document 4, Patent Document 5, etc.) are known. However, although the former rubber has excellent oil resistance and weather resistance, halogen tends to suppress the use of halogen in recent years because it emits a harmful gas with combustion, and thus halogen-free oil resistance and weather resistance have been obtained. Rubber is needed to be prepared. Further, as the latter rubber, although it is excellent in weather resistance, particularly ozone resistance, it is not sufficient in oil resistance and it is hard to say that it is excellent in oil resistance, weather resistance and mechanical properties in a well-balanced manner. Furthermore, the blending of elastomers has improved new properties and various properties.
A vulcanized rubber obtained by blending an unsaturated nitrile / conjugated diene-based copolymer and an acrylate-based copolymer is also known (Patent Document 6, Patent Document 7, Patent Document 8 and the like). But,
It is hard to say that this rubber also has excellent oil resistance, fuel oil resistance, weather resistance and mechanical properties in a well-balanced manner. From the above, there is a need for a rubber which does not contain halogen and is excellent in weather resistance, oil resistance and strength in a well-balanced manner, and a rubber composition which provides the same.

Acrylic rubber is a copolymer of an acrylic ester as a main component and a monomer which acts as a cross-linking point, and is generally used as a rubber which gives rubber products excellent in heat resistance, oil resistance and ozone resistance. Known, oil seal,
It is used as a molding material for O-rings and packing. In recent years, with the increasing performance of automobiles, the required performance cannot be satisfied at the heat resistance, oil resistance, and cold resistance of conventional rubber materials, and the development of rubber with more advanced functions has been required. Has been. For example, since the use environment of rubber parts becomes higher and higher, a fuel oil resistant rubber material having more excellent heat resistance is desired. Further, in the use of the sealing material, improvement in heat resistance, compression set and water resistance are strongly required. As the crosslinkable acrylic rubber, those having an active chlorine-containing monomer as a constituent at the cross-linking point and those having an epoxy group-containing monomer as a constituent are generally used. Those having a component as a component have a problem in terms of compression set of the crosslinked product, metal corrosion resistance, and the like, and those having an epoxy group-containing monomer as a component have a problem in that the crosslinking speed is slow. there were. Various crosslinkable monomers other than these have been studied, but with conjugated diene-based monomers such as butadiene and pentadiene, a crosslinking reaction occurs during polymerization, and a good polymer cannot be obtained.

Acrylic rubbers containing alkyl acrylate as a main component are nitrile rubbers, fluororubbers,
Compared with hydrin rubber, hydrogenated nitrile rubber, etc., the resistance to fuel oil was extremely poor, and it could not be used in the part in contact with fuel oil.

[0005]

[Patent Document 1] Japanese Patent Laid-Open No. 50-94063

[Patent Document 2] Japanese Patent Laid-Open No. 57-119943

[Patent Document 3] Japanese Patent Laid-Open No. 62-280244

[Patent Document 4] JP-A-62-59650

[Patent Document 5] JP-A-53-23342

[Patent Document 6] JP-A-55-104332

[Patent Document 7] Japanese Patent Laid-Open No. 57-25342

[Patent Document 8] Japanese Patent Laid-Open No. 1-297451

[0006]

DISCLOSURE OF THE INVENTION The present invention is a novel acryl which does not contain halogen, has oil resistance and heat resistance, is excellent in fuel oil resistance, mechanical strength, and has a low compression set. An object of the present invention is to provide a copolymer rubber, a method for producing the same, a rubber composition containing the same, an oil weatherproof rubber composition, and an oil weatherproof rubber.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a monomer having a specific cross-linking point and an unsaturated nitrile monomer are one component of the constituent monomer. It has been found that the vulcanized rubber obtained by using is excellent in physical properties, and has completed the present invention.

That is, the present invention provides the following acrylic copolymer rubber, a method for producing the same, and a rubber composition containing the same.
An oil resistant and weather resistant rubber composition and an oil resistant and weather resistant rubber are provided. [1] 40 to 91.9 mass% of a structural unit derived from at least one monomer selected from (A) acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester, and (B) unsaturated nitrile monomer 8 to 40% by mass of the structural unit derived from (C) at least one monomer selected from compounds represented by the non-conjugated cyclic polyene (C), the following general formula (1) and the following general formula (2). 0.1 to 20% by mass of the derived structural unit (provided that (A) +
(B) + (C) = 100 mass%), Mooney viscosity [ML
_{1 + 4} (100 ° C.)] is 10 to 200, and an acrylic acid ester copolymer rubber.

[Chemical 9] (In the formula, X ¹ represents a hydrogen atom or a methyl group, and n is 0 to
It is an integer of 10. )

[Chemical 10] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a hydrogen atom or an organic group having 1 to 10 carbon atoms in which hydrogen does not exist at the carbon adjacent to the double bond, and R ⁵ is a divalent group. An organic group having 1 to 10 carbon atoms in which hydrogen does not exist on the carbon adjacent to the heavy bond, X ² is a hydrogen atom, a —COOR ⁶ group (wherein R ⁶ is an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms). 14 alkoxyalkyl groups) or the following formula (3)

[Chemical 11] Is a group represented by

[Chemical 12] Or -O-, and n represents 1 or 0. [2] The acrylic acid ester according to the above [1], wherein the monomer forming the structural unit (A) is at least one selected from ethyl acrylate, n-butyl acrylate and methoxyethyl acrylate. Copolymer rubber. [3] 0.1 to 20 parts by mass of a structural unit derived from the epoxy group-containing unsaturated monomer (D) with respect to 100 parts by mass of the total of the structural units (A), (B) and (C). The acrylic acid ester-based copolymer rubber according to the above [1] or [2], which is contained.

[4] (a) 40 to 91.9% by mass of at least one monomer selected from alkyl acrylates and alkoxyalkyl acrylates,
(B) 8 to 40 mass% of unsaturated nitrile monomer, and (c)
0.1 to 20% by mass of at least one monomer selected from the compounds represented by the following general formula (1) and the following general formula (2), containing a non-conjugated cyclic polyene (provided that
(A) + (b) + (c) = 100% by mass) A monomer is copolymerized in the presence of a radical polymerization initiator to produce an acrylic ester copolymer rubber.

[Chemical 13] (In the formula, X ¹ represents a hydrogen atom or a methyl group, and n is 0 to
It is an integer of 10. )

[Chemical 14] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a hydrogen atom or an organic group having 1 to 10 carbon atoms in which hydrogen does not exist at the carbon adjacent to the double bond, and R ⁵ is a divalent group. An organic group having 1 to 10 carbon atoms in which hydrogen does not exist on the carbon adjacent to the heavy bond, X ² is a hydrogen atom, a —COOR ⁶ group (wherein R ⁶ is an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms). 14 alkoxyalkyl groups) or the following formula (3)

[Chemical 15] Is a group represented by

[Chemical 16] Or -O-, and n represents 1 or 0. )

[5] A rubber composition containing the acrylic ester copolymer rubber according to any one of the above [1] to [3] and sulfur and / or organic peroxide. [6] (X) 10 to 50% by mass of the acrylic acid ester-based copolymer rubber according to any one of the above [1] to [3]
And (Y) unsaturated nitrile-conjugated diene copolymer 90
50 to 50 mass% (however, (X) + (Y) = 100 mass%) is contained, The oil-resistant weather-resistant rubber composition characterized by the above-mentioned. [7] An oil-resistant and weather-resistant rubber obtained by crosslinking the rubber composition as described in [6] above, wherein the acrylic ester copolymer rubber (X) and the unsaturated nitrile / conjugated diene copolymer ( An oil-resistant and weather-resistant rubber characterized in that Y) is co-crosslinked. [8] The oil- and weather-resistant rubber according to the above [7], wherein the co-crosslinking is made of tetraalkyl thiuram disulfide having an alkyl group having 2 to 18 carbon atoms.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the copolymer rubber of the present invention will be specifically described below. The copolymer rubber of the present invention is
(A) 40 to 91.9 mass units of a structural unit derived from at least one kind of monomer (hereinafter, also referred to as “monomer (a)”) selected from acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester %, 8 to 40% by mass of the structural unit derived from (B) unsaturated nitrile monomer (hereinafter, also referred to as “monomer (b)”), (C) non-conjugated cyclic polyene, and general below. 0.1 to 20% by mass of a structural unit derived from at least one monomer selected from the compounds represented by formula (1) and the following general formula (2) (provided that (A) + (B) + (C) = 100% by mass) and the Mooney viscosity [ML _{1 + 4} (100 ° C.)] is 10 to 200.
Is characterized in that.

[Chemical 17] (In the formula, X ¹ represents a hydrogen atom or a methyl group, and n is 0 to
It is an integer of 10. )

[Chemical 18] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a hydrogen atom or an organic group having 1 to 10 carbon atoms in which hydrogen does not exist at the carbon adjacent to the double bond, and R ⁵ is a divalent group. An organic group having 1 to 10 carbon atoms in which hydrogen does not exist on the carbon adjacent to the heavy bond, X ² is a hydrogen atom, a —COOR ⁶ group (wherein R ⁶ is an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms). 14 alkoxyalkyl groups) or the following formula (3)

[Chemical 19] Is a group represented by

[Chemical 20] Or -O-, and n represents 1 or 0. )

Hereinafter, each component will be described more specifically. Examples of the alkyl acrylate ester of the monomer (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, and acrylic. Hexyl acid, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate and the like can be mentioned. These can be used alone or in combination of two or more. Of these, ethyl acrylate and n-butyl acrylate are particularly preferable in terms of oil resistance and flexibility of rubber products.

As the acrylic acid alkoxyalkyl ester of the monomer (a), for example, methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, acrylic acid Ethoxypropyl,
Examples thereof include butoxyethyl acrylate. These are 1
They may be used alone or in combination of two or more. Of these, methoxyethyl acrylate is particularly preferable in terms of cold resistance.

The constitutional ratio of the structural unit (A) constituting the acrylic ester copolymer rubber of the present invention [copolymerization ratio of the monomer (a)] is when the total of all structural units is 100% by mass. , 40 to 91.9% by mass, preferably 55
Is about 89% by mass. If this proportion is less than 40% by mass, the hardness of the obtained rubber product tends to be excessive and the rubber product tends not to have a suitable elastic state. On the other hand, this ratio is 9
If it exceeds 1.9 mass%, the oil resistance tends to be poor.

Examples of the unsaturated nitrile monomer (b) include acrylonitrile, methacrylonitrile,
Ethacrylonitrile, α-chloroacrylonitrile, α
-Fluoroacrylonitrile and the like can be mentioned. These can be used alone or in combination of two or more. Of these, acrylonitrile is particularly preferable in terms of fuel resistance.

The structural unit (B) constituting the acrylic ester copolymer rubber of the present invention has a constitution ratio [copolymerization ratio of the monomer (b)] of 8 to 40% by mass, preferably 10 to 3%.
It is 5% by mass. When the amount is less than 8% by mass, the fuel oil resistance of the obtained rubber product is insufficient, while when it exceeds 40% by mass, the hardness of the obtained rubber product tends to be high.

The monomer that becomes the structural unit (C) after copolymerization for introducing a crosslinking point is a non-conjugated cyclic polyene, a compound represented by the above general formula (1) or the above general formula (2). . These can be used alone or in combination of two or more.

Examples of the non-conjugated cyclic polyene include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene and 5-
Vinyl-2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene ,
5- (2-propenyl) -2-norbornene, 5- (3
-Butenyl) -2-norbornene, 5- (1-methyl-
2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-)
Butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2. -Norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5)
-Hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5-
(3-Ethyl-4-pentenyl), 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexecyl). ) -2-Norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5-
(1,2,3-Trimethyl-4-pentenyl) -2-norbornene and the like can be mentioned. These can be used alone or in combination of two or more. Of these, 5-ethylidene-2-norbornene is particularly preferable.

The compound represented by the general formula (1) is a dihydrodicyclopentadienyloxyethyl group-containing ester of unsaturated carboxylic acid.

[Chemical 21]

In the general formula (1), X ¹ represents a hydrogen atom or a methyl group. n is an integer of 0 to 10, and preferably 1 or 2. Examples of the dihydrodicyclopentadienyloxyethyl group-containing ester of unsaturated carboxylic acid represented by the above general formula (1) include dihydrodicyclopentadienyloxyethylene and the like and unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Synthesized by ester reaction with acid. Examples thereof include dihydrodicyclopentadienyl acrylate, dihydrodicyclopentadienyl methacrylate, dihydrodicyclopentadienyloxyethyl acrylate, dihydrodicyclopentadienyloxyethyl methacrylate, dihydrodicycloacrylate. Examples thereof include pentadienyloxyoxydiethyl, dihydrodicyclopentadienyloxydiethyl methacrylate and the like.
These can be used alone or in combination of two or more. Of these, dihydrodicyclopentadienyloxyethyl acrylate is particularly preferable in terms of workability and strength characteristics.

Examples of the compound represented by the above general formula (2) include vinyl acrylate, vinyl methacrylate,
1,1-dimethylpropenyl acrylate, 1,1-dimethylpropenyl methacrylate, 3,3-dimethylbutenyl acrylate, 3,3-dimethylbutenyl methacrylate, divinyl itaconate, divinyl maleate, divinyl fumarate, Vinyl 1,1-dimethylpropenyl ether, vinyl 3,3-dimethylbutenyl ether, 1-acryloyloxy-1-phenylethene, 1-acryloyloxy-2-phenylethene, 1-methacryloyloxy-1-phenylethene, 1 -Methacryloyloxy-2-phenylethene and the like. These can be used alone or in combination of two or more. Of these, vinyl acrylate and vinyl methacrylate are particularly preferable.

The structural unit (C) constituting the acrylic ester copolymer rubber of the present invention has a composition ratio of 0.1 to 20% by mass, preferably 100% by mass based on the total of all structural units. Is 1 to 10% by mass. If this ratio is less than 0.1% by mass or more than 20% by mass, the crosslinked product of the copolymer rubber obtained tends to be inferior in tensile strength and tensile elongation at break, and also tends to be inferior in hardness.

The structural proportions of the structural units (A), (B) and (C) are (A) / (B) / (C) = 40 to 91 when the total of all structural units is 100% by mass. 1.9 mass% /
8-40% by mass / 0.1-20% by mass, preferably 55-89.7% by mass / 10-35% by mass / 0.3-
It is 10% by mass.

Further, the acrylic ester copolymer rubber of the present invention preferably further contains (D) a structural unit derived from an epoxy group-containing unsaturated monomer. Examples of the epoxy group-containing unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, and methacryl glycidyl ether. These can be used alone or in combination of two or more. Of these, glycidyl methacrylate is particularly preferable.

The structural ratio of the structural unit (D) is preferably 0.1 when the total of all structural units is 100 parts by mass.
20 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 1 to 5 parts by mass. Within this range, the ozone resistance of the obtained rubber product can be improved.

If necessary, aromatic compounds such as styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, halogenated styrene, etc. may be used, as long as the properties of the acrylic ester copolymer rubber of the present invention are not impaired. Acrylamide, N-methylol acrylamide, N- (4
Amide compounds such as -anilinophenyl) acrylamide and N- (4-anilinophenyl) methacrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, acrylic acid esters of alicyclic alcohols such as cyclohexyl acrylate, acrylic acid A structural unit derived from an acrylic acid ester of an aromatic alcohol such as benzyl and an ester of an unsaturated carboxylic acid such as methacrylic acid, itaconic acid, fumaric acid and maleic acid with a lower saturated alcohol may also be included. Further, a structural unit derived from an amino group-containing ester of an unsaturated carboxylic acid such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate may be included.

The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the acrylic ester copolymer rubber of the present invention is 10 to 2
00, preferably 20 to 100. The polystyrene-equivalent weight average molecular weight of the acrylic ester copolymer rubber of the present invention measured by GPC (gel permeation chromatography) is preferably 10,000 or more, particularly preferably 100,000 to 80,000.
It is 10,000. Within this range, the processability of the rubber composition is sufficient and the strength of the rubber product obtained is excellent.

The acrylic acid ester-based copolymer rubber of the present invention can be crosslinked by a known method, like the generally known acrylic rubber.

The method for producing the acrylic acid ester-based copolymer rubber of the present invention comprises 40 to 91.9% by mass of the monomer (a).
And 8 to 40% by mass of the above-mentioned monomer (b), a non-conjugated cyclic polyene, and a monomer (c) of the compound represented by the general formula (1) or the general formula (2) (c) 0. 1 to 20% by mass (however, (a) + (b) + (c) = 1
(00% by mass) are copolymerized in the presence of a radical polymerization initiator. In addition, the epoxy group-containing unsaturated monomer and the like are copolymerized, if necessary.

Specifically, the copolymer rubber is obtained by copolymerizing a mixture containing the above-mentioned monomers in the presence of a radical polymerization initiator such as an inorganic or organic peroxide, an azo compound and a redox type initiator. It is synthesized by The amount of the radical polymerization initiator used is usually 0.001 to 2 parts by mass per 100 parts by mass of the total amount of the monomers. As the polymerization method, known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used, but emulsion polymerization is particularly preferable.

Examples of emulsifiers used in emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. Also,
A fluorinated surfactant can also be used. These emulsifiers may be used alone or in combination of two or more. Usually, anionic surfactants are frequently used, and for example, long-chain fatty acid salts having 10 or more carbon atoms, rosin acid salts, etc. are used. Specific examples thereof include capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid potassium salt and sodium salt.

Radical polymerization initiators include benzoyl peroxide, lauroyl peroxide and tert.
-Butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, di-te
Organic peroxides such as rt-butyl peroxide and dicumyl peroxide can be used. Further, a diazo compound such as azobisisobutyronitrile, an inorganic peroxide such as potassium persulfate, and a redox-based catalyst obtained by combining these peroxides with ferrous sulfate can also be used. These radical polymerization initiators may be used alone or in combination of two or more. Chain transfer agents can also be used to control the molecular weight of the copolymer rubber. As this chain transfer agent, alkyl mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan, carbon tetrachloride, thioglycols, diterpenes, terpinolene and γ-terpinenes can be used.

In the production of the acrylic ester copolymer rubber of the present invention, all the respective monomers, emulsifiers, radical polymerization initiators, chain transfer agents and the like are put into a reaction vessel all at once to start the polymerization. Alternatively, it may be added continuously or intermittently when the reaction is continued. This polymerization can be carried out at 0 to 100 ° C. using a reactor from which oxygen has been removed, and preferably at a polymerization temperature of 0 to 80 ° C.
During the reaction, the production conditions such as temperature or stirring can be changed appropriately. The polymerization system may be a continuous system or a batch system. The polymerization time is usually 0.01 to 3
After about 0 hours, after the polymerization is completed, the emulsion is treated with sodium chloride,
The target copolymer rubber is obtained by pouring the solution into an aqueous solution of an inorganic salt such as calcium chloride to coagulate the copolymer rubber, washing with water and drying.

The copolymer rubber obtained as described above is
The Mooney viscosity [ML _{1 + 4} (100 ° C.)] is preferably 10 to 200, and more preferably 20 to 10.
It is 0.

The rubber composition of the present invention is characterized by containing the above-mentioned acrylic acid ester copolymer rubber and sulfur and / or organic peroxide. Usually, an appropriate amount of a plasticizer, a filler, a reinforcing agent such as carbon black, a metal oxide, a softening agent, an antiaging agent, a processing aid, a flame retardant, an ultraviolet absorber and the like can be added.

Sulfur and organic peroxide are used as a crosslinking agent. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like. Further, a sulfur compound which releases active sulfur at the crosslinking temperature to crosslink, for example, morpholine disulfide, alkylphenol disulfide having 1 to 18 carbon atoms, tetraalkylthiuram disulfide having 1 to 18 carbon atoms, dipentamethylenethiuram tetrasulfide. Also, selenium dimethyldithiocarbamate or the like can be used as a vulcanization accelerator. Among these, tetraalkyl thiuram disulfide having 2 to 18 carbon atoms is preferable.

As the organic peroxide, for example, dicumyl peroxide, di-t-butyl peroxide, di-
t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl peroxide,
2,5-Dimethyl-2,5-di (t-butylperoxine) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-
2,5-mono (t-butylperoxy) -hexane,
Examples include α, α′-bis (t-butylperoxy-m-isopropyl) benzene and the like. Among them, dicumyl peroxide, di-t-butyl peroxide, di-t-
Butyl peroxy-3,3,5-trimethylcyclohexane is preferred. These organic peroxides can be used alone or in combination of two or more.

As the cross-linking agent, sulfur and organic peroxide may be used in combination. The amount of the cross-linking agent is usually 0.1 to 10 when the total amount of the rubber component is 100 parts by mass.
Parts by mass, particularly preferably 1 to 6 parts by mass.

When using the cross-linking agent, a cross-linking accelerator, a cross-linking aid and the like can be used. Specific examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide and N-oxydiethylene-2.
-Sulfenamide compounds such as benzothiazolylsulfenamide and N, N-diisopropyl-2-benzothiazolylsulfenamide; 2-mercaptobenzothiazole, 2- (2 ', 4'-dinitrophenyl) ) Thiazol compounds such as mercaptobenzothiazole, 2- (4'-morpholinodithio) benzothiazole and dibenzothiazyl disulfide; diphenylguanidine, diorsotolylguanidine, diorsonitrile guanidine,
Guanidine compounds such as orthonitrile biguanide and diphenylguanidine phthalate; acetaldehyde-
Aniline reaction product, butyraldehyde-aniline condensate,
Aldehyde amines such as hexamethylene tetramine and acetaldehyde ammonia, or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotrilthiourea. Compounds; thiuram-based compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetraoctylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di- Zinc n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, butyrate Zinc phenyl dithiocarbamate,
Examples thereof include dithioate-based compounds such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate; zanthate-based compounds such as zinc dibutylxanthate; compounds such as zinc white.

Specific examples of the crosslinking assistant include quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; diallyl phthalate and triallyl cyanurate. Examples thereof include allyl compounds such as G .; maleimide compounds; divinylbenzene and the like.

Examples of the plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate and diisodecyl phthalate. , Dimethyl adipate, diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate,
Diisobutyl azelate, dibutyl sebacate, di-
(2-Ethylhexyl) sebacate, diisooctyl sebacate and other fatty acid esters, trimellitic acid isodecyl ester, trimellitic acid octyl ester, trimellitic acid n-octyl ester, trimellitic acid isononyl ester Other than acid esters,
Di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate,
Trilauryl phosphate, tristearyl phosphate, tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like can be mentioned.
These may be used alone or in combination of two or more.

As the filler, for example, silica, heavy calcium carbonate, gourd powder, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyrolite clay, Silane-treated clay, Synthetic calcium silicate, Synthetic magnesium silicate, Synthetic aluminum silicate, Magnesium carbonate, Aluminum hydroxide, Magnesium hydroxide, Magnesium oxide, Kaolin, Sericite, Talc, Fine talc, Wollastonite, Zeolite, Zonotonite, Asbestos, PMF (Proce
ssed Mineral Fiber, sepiolite, potassium titanate, elestadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, silas balun, carbon balun, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, etc. To be These may be used alone or in combination of two or more.

Examples of carbon black as an example of the reinforcing agent include SAF carbon black, ISAF carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, and acetylene carbon. Examples include black and Ketjen black. These may be used alone or in combination of two or more.

Examples of the metal oxide include zinc white, activated zinc white, surface-treated zinc white, zinc carbonate, complex zinc white, complex active zinc white, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, ultrafine water. Calcium oxide,
Examples thereof include lead monoxide, red lead and lead white. These may be used alone or in combination of two or more.

Examples of the softener include petroleum-based softeners, vegetable oil-based softeners, and sub-softeners. These may be used alone or in combination of two or more. Examples of the petroleum-based softening agent include aromatic-based, naphthene-based, and paraffin-based softening agents. Examples of plant softeners include castor oil, cottonseed oil, linseed oil, rapeseed oil,
Examples include soybean oil, palm oil, coconut oil, peanut oil, and wax. Examples of the sub include black sub, white sub, candy sub, and the like.

Examples of the antiaging agent include naphthylamine type, diphenylamine type, p-phenylenediamine type, quinoline type, hydroquinone derivative type, mono, bis,
Examples include tris, polyphenol-based, thiobisphenol-based, hindered phenol-based, phosphite-based, imidazole-based, dithiocarbamic acid nickel salt-based, and phosphoric acid-based antioxidants. These may be used alone or in combination of two or more.

Examples of the processing aids include stearic acid, oleic acid, lauric acid, zinc stearate, calcium stearate, potassium stearate, sodium stearate, stearylamine and the like. These may be used alone or in combination of two or more.

The rubber composition of the present invention may contain other rubber as a rubber component. Other rubbers are not particularly limited, but acrylic ester copolymer rubbers other than the present invention, styrene-butadiene copolymer rubbers, butadiene rubbers, isoprene rubbers, butadiene / isoprene copolymer rubbers, butadiene / styrene / isoprene copolymer rubbers. , Acrylonitrile / butadiene copolymer rubber, butyl rubber, natural rubber, chloroprene rubber and the like can be used. It can also be used with an olefin resin such as polyethylene or polypropylene.

The rubber composition of the present invention can be crosslinked with sulfur and / or organic peroxide to obtain a crosslinked rubber having oil resistance, heat resistance, fuel oil resistance, and tensile strength. .

The oil-resistant and weather-resistant rubber composition of the present invention comprises the above acrylic ester copolymer rubber (hereinafter referred to as "component (X)".
Also called. ) 10 to 50 mass% and unsaturated nitrile-conjugated diene-based copolymer (hereinafter, also referred to as "component (Y)") 90 to 50 mass% (however, (X) + (Y) = 1)
00% by mass).

The component (Y) is not particularly limited as long as it is a polymer containing a structural unit derived from an unsaturated nitrile monomer and a structural unit derived from a conjugated diene monomer. Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferable. These may be used alone or in combination of two or more.

Examples of the conjugated diene-based monomer include 1,3-butadiene and isoprene (2-methyl-
1,3-butadiene), 2,3-dimethyl-1,3-butadiene, chloroprene (2-chloro-1,3-butadiene) and the like. These are 1 type alone or 2
One or more species can be used in combination.

When the total amount of the structural unit (P) derived from the unsaturated nitrile monomer and the structural unit (Q) derived from the conjugated diene monomer is 100% by mass. , Preferably (P) / (Q) = 30 to 70
Mass% / 70 to 30 mass%, more preferably (P) /
(Q) = 40-60% by mass / 60-40% by mass.
When the content of the structural unit (P) is less than 30% by mass, oil resistance and the like tend to be lowered. On the other hand, when the content exceeds 70% by mass, the productivity may be reduced and the obtained rubber product may be hard.

The component (Y) may be obtained by copolymerizing other monomer in addition to the unsaturated nitrile monomer and the conjugated diene monomer. Examples of other monomers include aromatic vinyl monomers and (meth) acrylic acid alkyl esters. These can be used alone or in combination of two or more.

Examples of the aromatic vinyl monomer include styrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
Methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t
Examples include ert-butyl styrene and tert-butoxy styrene. These monomers may be used alone or in combination of two or more.

The aromatic vinyl monomer may be a compound having a functional group such as an amino group and a hydroxyl group. Examples of the aromatic vinyl monomer having an amino group include N, N-dimethyl-p-aminostyrene, N, N
-Diethyl-p-aminostyrene, dimethyl (p-vinylbenzyl) amine, diethyl (p-vinylbenzyl)
Amine, dimethyl (p-vinylphenethyl) amine, diethyl (p-vinylphenethyl) amine, dimethyl (p
-Vinylbenzyloxymethyl) amine, dimethyl [2
-(P-vinylbenzyloxy) ethyl] amine, diethyl (p-vinylbenzyloxymethyl) amine, diethyl [2- (p-vinylbenzyloxy) ethyl] amine, dimethyl (p-vinylphenethyloxymethyl) amine, dimethyl [2- (p-vinylphenethyloxy)
Ethyl] amine, diethyl (p-vinylphenethyloxymethyl) amine, diethyl [2- (p-vinylphenethyloxy) ethyl] amine, 2-vinylpyridine, 3
Examples thereof include compounds having a tertiary amino group such as vinyl pyridine and 4-vinyl pyridine. These monomers are 1
Only one species may be used, or two or more species may be used in combination.

Examples of the aromatic vinyl monomer having a hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, Examples thereof include p-hydroxy-α-methylstyrene and p-vinylbenzyl alcohol. These monomers may be used alone or in combination of two or more.

Examples of the above-mentioned (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, and (meth) acrylic. Acid n-butyl, (meth) acrylic acid n-amyl, (meth)
Examples include n-hexyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. These monomers may be used alone,
You may use 2 or more types together.

The (meth) acrylic acid alkyl ester may be a compound having a functional group such as an amino group, a hydroxyl group, an epoxy group and a carboxyl group. Examples of the (meth) acrylic acid alkyl ester having an amino group include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and 2-diethylamino (meth) acrylate. Ethyl, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-meth) acrylic acid. Examples include n-propylamino) propyl, (meth) acrylic acid 3-dimethylaminopropyl, (meth) acrylic acid 3-diethylaminopropyl, and (meth) acrylic acid 3- (di-n-propylamino) propyl. These monomers may be used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester having a hydroxyl group include (meth) acrylic acid 2-
Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- (meth) acrylic acid Hydroxyalkyl (meth) acrylic acids such as hydroxybutyl, and polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 2).
Examples thereof include mono (meth) acrylic acid esters of 3). These monomers may be used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester having an epoxy group include glycidyl (meth) acrylate and 3,4-oxycyclohexyl (meth) acrylate. These monomers may be used alone or in combination of two or more. Examples of the (meth) acrylic acid alkyl ester having a carboxyl group include a non-polymerizable polyvalent carboxylic acid such as phthalic acid, succinic acid, and adipic acid, and a non-polymerizable polycarboxylic acid such as 2-hydroxyethyl (meth) acrylate. Examples thereof include monoesters with saturated compounds and salts thereof. These monomers may be used alone or in combination of two or more.

The above-mentioned other monomers can be copolymerized within a range that does not impair the characteristics of the resulting unsaturated nitrile / conjugated diene-based copolymer. When the total amount of the conjugated diene-based monomer is 100 parts by mass, it is preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less.

Mooney viscosity [ML] of the above component (Y)
_{1 + 4} (100 ° C.)] is preferably 30 to 150, more preferably 50 to 100. When the Mooney viscosity is less than 30, the tensile strength tends to decrease.
On the other hand, if it exceeds 150, the workability tends to decrease.

Content ratio (X) / (Y) of component (X) and component (Y) constituting the oil resistant and weather resistant rubber composition of the present invention.
Is 10 to 5 when the total of these is 100% by mass.
0% by mass / 90 to 50% by mass, preferably 20 to
It is 40 mass% / 80-60 mass%. The above component (X)
If the content of is too large, the tensile strength tends to decrease.

The oil-resistant and weather-resistant rubber composition of the present invention may be blended with the various additives exemplified above.

A rubber product using the rubber composition and the oil-resistant and weather-resistant rubber composition of the present invention can be manufactured, for example, as follows. First, the acrylic ester copolymer rubber of the present invention, a filler, a reinforcing agent such as carbon black, a softening agent, and other compounding agents other than a cross-linking agent are mixed at 70 to 180 ° C. using a kneading machine such as a Banbury mixer. Knead at the temperature of. Then, the kneaded product is cooled, and a crosslinking agent such as sulfur and a crosslinking accelerator are further mixed therein using a Banbury mixer, a mixing roll or the like, and molded into a predetermined shape. Then, it is crosslinked at a temperature of 130 to 200 ° C to obtain a desired crosslinked rubber, that is, a rubber product.

The oil resistant and weather resistant rubber of the present invention is obtained by crosslinking the oil resistant and weather resistant rubber composition, and is characterized in that the component (X) and the component (Y) are co-crosslinked. . The composition used for obtaining the oil resistant and weather resistant rubber contains additives such as a crosslinking agent selected from sulfur and / or organic peroxides. Since this composition contains the above component (X) and the above component (Y) having an unsaturated bond,
By the "crosslinking" step, co-crosslinking via an unsaturated bond can be performed.

Upon co-crosslinking, it is preferable to use sulfur as a crosslinking agent, and it is more preferable to use a tetraalkyl thiuram disulfide having 2 to 18 carbon atoms in combination. The method for producing the oil resistant and weather resistant rubber is not particularly limited,
The same applies to the description regarding the production of the rubber product.

The oil-resistant and weather-resistant rubber of the present invention has oil resistance, heat resistance, fuel oil resistance and tensile strength, and by utilizing these effects, an oil cooler hose, air duct hose, power steering hose, control hose, Various hose materials such as intercooler hoses, torque converter hoses, oil return hoses, heat-resistant hoses, fuel hose materials, bearing seals, bulk stem seals, various oil seals, O-rings, packing materials, sealing materials such as gaskets, various diaphragms, rubber plates It can be suitably used for a belt, an oil level gauge, a hose masking, a coating material such as a pipe heat insulating material, a roll and the like.

[0070]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The parts and% in the examples and comparative examples are based on mass unless otherwise specified.

1. Example 1 Production of Acrylic Ester Copolymer Rubber A monomer mixture consisting of 83 parts of ethyl acrylate, 12 parts of acrylonitrile and 5 parts of dihydrodicyclopentadienyloxyethyl acrylate (DCPOEA), and 4 parts of sodium lauryl sulfate. , 200 parts of water and 0.2 part of potassium persulfate were charged in a nitrogen-replaced stainless reactor and polymerized at 50 ° C. When the polymerization conversion rate reached almost 100%, 0.5 part of N, N-diethylhydroxylamine was added to the reaction system to stop the copolymerization reaction (reaction time 15 hours). Then, the reaction product (latex) was taken out, and an aqueous calcium chloride solution (0.25%) was added to the reaction product to solidify the copolymer rubber. The coagulated product was thoroughly washed with water and then dried at about 90 ° C. for 3 hours to give a Mooney viscosity [ML _{1 + 4} (100
C)] was 72 to obtain a copolymer rubber R-1 (see Table 1).

Examples 2 to 9 and Comparative Examples 1 to 3 Copolymer rubbers R-2 to R-12 were obtained in the same manner as in Example 1, except that the monomers shown in Table 1 were polymerized in a predetermined amount. It was Scanning differential thermal analyzer (DS) for all copolymer rubbers
C) The measurement was carried out, and a single glass transition point different from that of the homopolymer of the monomers constituting them was observed, and it was confirmed that the obtained copolymer rubber was a random copolymer. .

[0073]

[Table 1]

2. Preparation and Evaluation of Compositions Containing Copolymer Rubber Examples 10-18, Comparative Examples 4-6 100 of Copolymer Rubbers R-1 to R-12 obtained above.
Part, stearic acid (manufactured by Kao Corporation) 1.0 part, carbon black (trade name "SEAST 116", manufactured by Tokai Carbon Co.)
50 parts, zinc white 5.0 parts, adipic acid ether ester plasticizer (trade name "RS107", manufactured by Asahi Denka Kogyo Co., Ltd.) 1
5 parts, sulfur (manufactured by Tsurumi Chemical Co., Ltd.) 2.0 parts, tetraoctyl thiuram disulfide as a vulcanization accelerator (I) (trade name "NOXCELLER TOT-N", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 2.0 parts, N-cyclohexyl-2-benzothiazolylsulfenamide (trade name "NOXCELLER CZ", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) as a vulcanization accelerator (II) 1.0
Parts, and 0.5 parts of 2-mercaptobenzothiazole (trade name "NOXCELLER M", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) as a vulcanization accelerator (III) are kneaded with a roll to prepare a composition at 170 ° C. A vulcanized rubber sheet was produced by press vulcanizing for 20 minutes and the physical properties thereof were evaluated. The results are shown in Tables 2 and 3.

The evaluation of the vulcanized rubber was based on the following method. (A) Tensile breaking strength T _B and tensile breaking elongation E _B : JIS
It measured based on K6251. (B) Hardness H _A : Based on JIS K6253 (type A durometer hardness test). (C) Compression set C _S : According to JIS K6262, heat treatment was performed at 100 ° C. for 22 hours, and the value after 25% compression was measured. (D) Fuel oil resistance: in accordance with JIS K6258, Fu
Using the el C test oil and the Fuel C test oil mixed with ethanol, the volume change rate (ΔV) was determined by a dipping test at 40 ° C. for 48 hours.

[0076]

[Table 2]

[0077]

[Table 3]

From Table 2, Examples 10 to 18 using compositions containing acrylic ester type copolymer rubbers R-1 to R-5 are shown.
Is excellent in mechanical strength, compression set, and fuel oil resistance, and in particular, it is excellent in alcohol-added fuel oil resistance. On the other hand, Comparative Example 4 using the composition containing the acrylic ester copolymer rubber R-10 is inferior in fuel oil resistance and mechanical strength because it does not contain a structural unit derived from an unsaturated nitrile monomer. In Comparative Example 5 using the composition containing the acrylic ester copolymer rubber R-11, the content of the structural unit derived from the unsaturated nitrile monomer was small, and thus the fuel oil resistance,
Poor mechanical strength. Further, Comparative Example 6 using the composition containing the acrylic ester-based copolymer rubber R-12 is too high in hardness and poor in flexibility because the content of the structural unit derived from the unsaturated nitrile monomer is too large. I understand.

3. Preparation and Evaluation of Oil-Resistant and Weather-Resistant Rubber Compositions Examples 19 to 24, Comparative Examples 7 to 18 The following acrylic ester copolymer rubbers were mixed in the ratios shown in Tables 4 to 8 and mixed in a Banbury mixer. A kneaded roll was used to prepare an oil-resistant and weather-resistant rubber composition, which was preformed and then press-vulcanized at 170 ° C. for 10 minutes to produce a vulcanized rubber sheet.

The blended raw materials used are as follows. "R-13": An acrylic ester-based copolymer rubber comprising 87% by mass of ethyl acrylate, 10% by mass of acrylonitrile and 3% by mass of 5-ethylidene-2-norbornene. "R-14": An acrylic ester copolymer rubber comprising 72% by mass of ethyl acrylate, 25% by mass of acrylonitrile and 3% by mass of dicyclopentadienyloxyethyl acrylate. [R-15]; 71% by mass of ethyl acrylate, 25% by mass of acrylonitrile, 1% by mass of ethylene glycol dimethacrylate, and 3-ethylidene-2-norbornene 3
It is an acrylic acid ester-based copolymer rubber composed of mass%. "R-16": an acrylic ester copolymer rubber comprising 84% by mass of ethyl acrylate, 10% by mass of acrylonitrile, 3% by mass of dicyclopentadienyloxyethyl acrylate and 3% by mass of allyl glycidyl ether. "R-17": An acrylic ester copolymer rubber composed of 69% by mass of ethyl acrylate, 25% by mass of acrylonitrile, 3% by mass of dicyclopentadienyloxyethyl acrylate and 3% by mass of allyl glycidyl ether. "R-18": An acrylic ester copolymer rubber composed of 97% by mass of ethyl acrylate and 3% by mass of dicyclopentadienyloxyethyl acrylate. "R-19": An acrylic ester copolymer rubber composed of 95% by mass of ethyl acrylate, 3% by mass of dicyclopentadienyloxyethyl acrylate and 2% by mass of ethylene glycol dimethacrylate.

"N217SH"; NBR (trade name "N2SH"
17SH ", manufactured by JSR), the acrylonitrile content is 4
7 mass%, Mooney viscosity [ML _{1 + 4} (100 ° C.)] is about 70. "NE61"; NBR / EPDM alloy (trade name "NE
61 ", manufactured by JSR). "N230S"; NBR (Product name "N230S", JS
Manufactured by R Co., Ltd.), the acrylonitrile content is 35% by mass, and the Mooney viscosity [ML _{1 + 4} (100 ° C.)] is 56. "NV72"; NBR (trade name "NV72", manufactured by JSR), medium and high AN, Mooney viscosity [ML _{1 + 4} (100
C)] is 75. "Super high AN-
NV ”; the above“ N217SH ”and NBR (trade name“ N
280 ", manufactured by JSR) and polyvinyl chloride (trade name" PVC3000H ", manufactured by Taiyo PVC Co., Ltd.) in a mass ratio of 6
It is a rubber component mixed at 5: 5: 30. "AREX117"; a chlorine-based acrylic ester copolymer rubber comprising 99% by mass of ethyl acrylate and 1% by mass of vinyl chloroacetate. "TN80"; Fluorine rubber (Product name "Technoflon TN
80 ", manufactured by Monte).

"Carbon black (I)"; MAF carbon (trade name "Seast 116", manufactured by Tokai Carbon Co., Ltd.). "Carbon black (II)"; FT-based carbon black (trade name "Asahi Thermal", manufactured by Asahi Carbon Co., Ltd.). "Plasticizer (I)"; adipic acid ether ester plasticizer (trade name "RS107", manufactured by Asahi Denka Kogyo Co., Ltd.). "Plasticizer (II)"; polyetherester plasticizer (trade name "RS735", manufactured by Asahi Denka Kogyo Co., Ltd.). "Stearic acid"; manufactured by Kao Corporation. "Zinc oxide"; trade name "ZnO # 2", manufactured by Sakai Chemical Co., Ltd. "Magnesium oxide"; trade name "MgO # 150", manufactured by Kyowa Chemical Co., Ltd. "Calcium hydroxide"; product name "Calbit", manufactured by Omi Chemical Co., Ltd. "Softener"; naphthenic oil (trade name "Fuccol
Flex 2050N ", manufactured by Fuji Kosan Co., Ltd.). "Sulfur (I)"; manufactured by Tsurumi Chemical Co., Ltd. "Sulfur (II)"; sulfur (trade name "Salfax PM
C ", manufactured by Tsurumi Chemical Co., Ltd.). "Organic peroxide"; dicumyl peroxide (trade name "DCP40", manufactured by NOF CORPORATION). "Vulcanization accelerator (I)"; (Brand name "NOXCELLER TOT-
N ", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.). "Vulcanization accelerator (II)";
Z ", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.). "Vulcanization accelerator (III)"; (trade name "NOXCELLER M", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.). "Vulcanization accelerator (IV)"; Tetraethyl thiuram disulfide (trade name "NOXCELLER TET", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.). "Vulcanization accelerator (V)": Tetramethylthiuram disulfide (trade name "NOXCELLER TT", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.). "Crosslinking agent (I)"; FKM crosslinking agent (trade name "Technoflon M1", manufactured by Monte Corporation). "Crosslinking agent (II)"; FKM crosslinking agent (trade name "Technoflon M2", manufactured by Monte Corporation). "Sodium stearate"; Yoneyama Chemical Co., Ltd. "Potassium stearate"; manufactured by NOF CORPORATION.

Evaluation of the rubber composition and the vulcanized rubber was based on the following methods. The results are shown in Tables 4 to 8. (A) Mooney viscosity: Measured at a temperature of 100 ° C. according to JIS K6300. (B) Normal state physical properties: In accordance with JIS K6251, tensile breaking strength T _B and tensile breaking elongation E _B , JIS K
The hardness H _A was measured according to 6253. (C) Heat aging test: 10 according to JIS K6257
Heat treatment was performed at 0 ° C. for 70 hours, and tensile strength at break, tensile elongation at break and hardness were measured. (D) Oil resistance: 100 ° C. according to JIS K6258
After immersing in IRM903 oil for 70 hours, the tensile strength at break, tensile elongation at break, hardness and rate of change in volume were measured. (E) Fuel oil resistance: 40 in accordance with JIS K6258
After being immersed in Fuel C at 48 ° C. for 48 hours, the tensile breaking strength, tensile breaking elongation, hardness and volume change rate were measured. (F) Low temperature impact embrittlement test: In accordance with JIS K6261. (G) Compression set C _S : According to JIS K6262, heat treatment was performed at 100 ° C. for 22 hours, and the value after 25% compression was measured. (H) Ozone resistance: According to JIS K6259. The sample was extended by 20%, exposed to an air atmosphere having an ozone concentration of 50 pphm and 40 ° C. for 200 hours, and the presence or absence of cracks was visually determined.

[0084]

[Table 4]

[0085]

[Table 5]

[0086]

[Table 6]

[0087]

[Table 7]

[0088]

[Table 8]

From Tables 6 to 8, Comparative Example 7 is an example in which only NBR / EPDM alloy was used as the rubber component, and the volume change rate of the vulcanized rubber due to the fuel oil resistance was 101%.
And very expensive. In Comparative Examples 8 and 9, as rubber components, N different in acrylonitrile content and Mooney viscosity were used.
This is an example using BR, and both have poor ozone resistance. Comparative Example 13 was also a vulcanized rubber composed of a rubber composition similar to Comparative Example 9, but also showed the same physical properties. Comparative Example 10
Comparative Example 12 is also an example using a rubber component outside the scope of the present invention, and the volume change rate of the vulcanized rubber due to the fuel oil resistance is slightly high. Comparative Example 12 has a tensile breaking strength of 10MP.
It did not reach a. Comparative Example 14 has an acrylic ester copolymer rubber (R- having a structural unit composition outside the scope of the present invention).
18), and the content ratio of the two rubber components is outside the range of the present invention, and the tensile rupture strength is poor. Comparative Example 17 in which the structural unit composition uses an acrylic ester copolymer rubber (R-18) outside the range of the present invention and the content ratio of the two rubber components is within the range of the present invention, the tensile breaking strength is It recovers slightly, but the volume change rate of vulcanized rubber due to fuel oil resistance is slightly high. Comparative Example 18 also showed the same physical properties as Comparative Example 17. On the other hand, from Table 4 and Table 5, Examples 19 to 24
Indicates that the two rubber components relating to the present invention are sufficiently co-crosslinked and the tensile breaking strength is as high as 13.2 to 19.2 MPa,
Furthermore, the tensile elongation at break is excellent at 400% or more. It has a relatively low volume change rate, excellent oil resistance, and excellent balance with various physical properties such as low temperature impact resistance, compression set, and ozone resistance.

[0090]

According to the acrylic ester copolymer rubber of the present invention, a vulcanized rubber product having oil resistance and heat resistance due to crosslinking, excellent fuel oil resistance, mechanical strength, and low compression set is obtained. can get. Structural units derived from monomers selected from acrylic acid alkyl esters and acrylic acid alkoxyalkyl esters, structural units derived from unsaturated nitrile monomers, and non-conjugated cyclic polyenes, the above general formula (1) and the above general formula In addition to the acrylic ester copolymer rubber composed of a structural unit derived from a monomer selected from the compound represented by (2), a structural unit derived from an epoxy group-containing unsaturated monomer is further contained. By doing so, ozone resistance and tensile strength can be improved. Further, according to the method for producing an acrylic copolymer rubber of the present invention, the above acrylic copolymer rubber can be easily produced.

According to the rubber composition of the present invention, sulfur and / or
Alternatively, by crosslinking with an organic peroxide, a crosslinked rubber having oil resistance, heat resistance, fuel oil resistance, and tensile strength can be obtained. Further, according to the oil-resistant and weather-resistant rubber composition of the present invention, by crosslinking, a crosslinked rubber excellent in ozone resistance, oil resistance, heat aging resistance and processability, and also excellent in tensile strength, tensile elongation at break and hardness. Can be obtained. The oil-resistant and weather-resistant rubber of the present invention, because the acrylic ester-based copolymer rubber and the unsaturated nitrile-conjugated diene-based copolymer are co-crosslinked, ozone resistance, oil resistance, heat aging resistance and processability It is also excellent in tensile strength, tensile elongation at break and hardness, and its performance balance is extremely good. In particular,
When co-crosslinked with a tetraalkylthiuram disulfide having an alkyl group having 2 to 18 carbon atoms, a particularly high-performance crosslinked rubber can be obtained. Utilizing the above effects, the present invention provides various hose materials such as oil cooler hoses, air duct hoses, power steering hoses, control hoses, intercooler hoses, torque converter hoses, oil return hoses, heat resistant hoses, bearing seals, bulk stem seals. , Various oil seals,
Sealing materials such as O-rings, packings, gaskets, various diaphragms, rubber plates, belts, oil level gauges,
It is useful for hose masking, coating materials such as heat insulation materials for pipes, and rolls.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 9/02 C08L 9/02 33/08 33/08 (72) Inventor Katsutaka Yokoi Tsukiji, Chuo-ku, Tokyo 2 C-number 11-24 J-F Co., Ltd. F term (reference) 4J002 AC071 BG042 DA046 EK006 EV046 FD146 GM00 GN00 4J100 AL02P AL08P AL09P AM01Q AM02Q AR15R AR16R AS11R AS13R BA08P BA16R BA20R BC27P CA05 DA09 DA36 DA36 DA40

Claims (8)

[Claims] 1. A structural unit derived from at least one monomer selected from (A) acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester is 40-9.
1.9% by mass, (B) 8 to 40% by mass of a structural unit derived from an unsaturated nitrile monomer, (C) a non-conjugated cyclic polyene, the following general formula (1) and the following general formula (2). 0.1 to 20% by mass of a structural unit derived from at least one monomer selected from compounds represented by
(A) + (B) + (C) = 100 mass%), Mooney viscosity [ML _{1 + 4} (100 ° C.)] is 10 to 200, and an acrylic acid ester copolymer rubber. [Chemical 1] (In the formula, X ¹ represents a hydrogen atom or a methyl group, and n is 0 to
It is an integer of 10. ) [Chemical 2] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a hydrogen atom or an organic group having 1 to 10 carbon atoms in which hydrogen does not exist at the carbon adjacent to the double bond, and R ⁵ is a divalent group. An organic group having 1 to 10 carbon atoms in which hydrogen does not exist on the carbon adjacent to the heavy bond, X ² is a hydrogen atom, a —COOR ⁶ group (wherein R ⁶ is an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms). 14 alkoxyalkyl groups) or the following formula (3): And Y is a group represented by Or -O-, and n represents 1 or 0. ) 2. The acrylic acid ester according to claim 1, wherein the monomer forming the structural unit (A) is at least one selected from ethyl acrylate, n-butyl acrylate and methoxyethyl acrylate. Copolymer rubber. 3. The structural units (A), (B) and (C)
The acrylic ester copolymer rubber according to claim 1 or 2, further comprising 0.1 to 20 parts by mass of the structural unit derived from the epoxy group-containing unsaturated monomer (D) with respect to 100 parts by mass in total. . 4. (a) 40 to 91.9% by mass of at least one monomer selected from alkyl acrylate and alkoxyalkyl acrylate, and (b)
8 to 40 mass% of unsaturated nitrile monomer, (c) non-conjugated cyclic polyene, the following general formula (1) and the following general formula (2)
0.1 to 20% by mass of at least one monomer selected from compounds represented by the formula (provided that (a) +
(B) + (c) = 100% by mass) A monomer is copolymerized in the presence of a radical polymerization initiator. [Chemical 5] (In the formula, X ¹ represents a hydrogen atom or a methyl group, and n is 0 to
It is an integer of 10. ) [Chemical 6] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a hydrogen atom or an organic group having 1 to 10 carbon atoms in which hydrogen does not exist in the carbon adjacent to the double bond, and R ⁵ is a divalent group. An organic group having 1 to 10 carbon atoms in which hydrogen does not exist in the carbon adjacent to the heavy bond, X ² is a hydrogen atom, a —COOR ⁶ group (wherein R ⁶ is an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms). 14 alkoxyalkyl group) or the following formula (3): And Y is a group represented by Or -O-, and n represents 1 or 0. ) 5. A rubber composition comprising the acrylic ester copolymer rubber according to claim 1 and sulfur and / or an organic peroxide. 6. (X) 10 to 50% by mass of the acrylic acid ester-based copolymer rubber according to any one of claims 1 to 3.
And (Y) unsaturated nitrile-conjugated diene copolymer 90
50 to 50 mass% (however, (X) + (Y) = 100 mass%) is contained, The oil-resistant weather-resistant rubber composition characterized by the above-mentioned. 7. An oil and weather resistant rubber obtained by crosslinking the rubber composition according to claim 6, wherein the acrylic ester copolymer rubber (X) and the unsaturated nitrile / conjugated diene copolymer are used. (Y) is co-crosslinked, and is oil-resistant and weather-resistant rubber. 8. The oil resistant weather resistant rubber according to claim 7, wherein the co-crosslinking is made of tetraalkyl thiuram disulfide having an alkyl group having 2 to 18 carbon atoms.