Acrylic Elastomer Copolymer

Abstract

An acrylic elastomer copolymer constituted by containing a copolymerizable anti-aging agent represented by general formula (I) (R1: C1-20 aliphatic hydrocarbon group, C7-20 aralkyl group, or C2-20 acyl group, R2: hydrogen atom or methyl group, A: direct bond or divalent organic group, B: direct bond, oxygen atom, sulfur atom, sulfoxide group, or sulfone group, x: 0 or 1), an alkyl (meth)acrylate monomer and / or alkoxyalkyl (meth)acrylate monomer, and a crosslinking site monomer. This acrylic elastomer copolymer is stabilized against thermo-oxidative degradation.

Description

[Technical Field]

[0001] The present invention relates to acrylic elastomeric copolymers, and more particularly to acrylic elastomeric copolymers stabilized against thermo-oxidative degradation. [Background technology]

[0002] Regulations on emissions of carbon dioxide, NOx gases, and other gases emitted from internal combustion engines, such as gasoline and diesel engines, are becoming increasingly strict. To address these demands, automobile engines are being required to have higher power output, higher thermal efficiency, and reduced or harmless exhaust gases, which has resulted in rising temperatures inside the engine compartment. Accordingly, polymeric materials used in the vicinity of engines, such as rubber and plastics, are being required to have even higher heat resistance.

[0003] As a specific example, vehicles equipped with turbocharger systems to improve engine fuel efficiency are becoming more common. The air guided from the turbocharger to the intercooler and engine is at high temperature and pressure, so the rubber hose material that transports this air must have high heat resistance.

[0004] As the polymeric materials used in automobile engines are required to be used in higher temperatures and have longer life spans, it is common practice to add appropriate antioxidants (antioxidants) to rubber or plastic components to improve their heat resistance.

[0005] Phenol-based antioxidants and amine-based antioxidants are used as antioxidants for rubber members, and amine-based antioxidants are used particularly for rubber members used in higher temperature environments.

[0006] For example, in the case of acrylic rubber, an amine-based antioxidant, typified by 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, is used as the antioxidant (Patent Documents 1 to 6).

[0007] However, even the above-mentioned amine-based antioxidants cannot fully satisfy the current requirements for heat resistance and other problems.

[0008] In recent years, phenothiazine-based antioxidants have been considered effective as antioxidants for rubber materials, and Patent Document 7 describes a rubber material that is excellent in vulcanization properties, mechanical properties, and heat aging properties and is particularly suitable for use as vibration-proof rubber, containing (A) a diene rubber, (B) a bismaleimide compound, and (C) the following phenothiazine compound: TIFF0007719880000001.tif27165R 1 , R 2 : Hydrogen atom, optionally substituted with an aromatic ring C1 to C8 alkyl groups, Alkoxy group, halogen atom, cyano group R 3 : Hydrogen atom, C1-C6 chain or cyclic Alkyl group, vinyl group, aromatic group m, n: 0 to 2 Phenothiazine compounds in which the sulfur atom at the 5-position is -SO2- are also known and are described in, for example, Patent Document 8.

[0009] Patent Document 8 describes a fused heterocyclic compound represented by the following general formula and an organic material composition containing the same, and states that the compound can impart high processing stability, heat resistance, and long life to organic materials such as polymers that are susceptible to oxidative, thermal, or light-induced degradation. TIFF0007719880000002.tif28165Y: Chemical single bond, -S(=O)-, -SO2- R a , R b : C1 to C which may have a substituent 30 organic group Z a , Z b : Chemical single bond, -SO2- X 1 , X 2 : a hydrogen atom, a halogen atom, an alkyl group, Cyano group, nitro group, -OR1 , -O-CO-R 1 , -CO-OR 1 , -O-CO-OR 1 , -NR 2 R 3 , -NR 2 -CO-R 1 , -CO-NR 2 R 3 , -O-CO-NR 2 R 3 n, m: 0 to 2, but either one is not 0

[0010] Furthermore, studies have been conducted to increase the molecular weight and melting point of amine-based antioxidants, but this has led to problems such as a decrease in dispersibility in rubber and migration within the rubber.

[0011] Additionally, antioxidants having a polymerizable unsaturated group have been marketed with the aim of preventing the evaporation of antioxidants and extending the life of rubber parts in high-temperature environments.

[0012] For example, Nocrac G-1 (Ouchi Shinko Chemical Industry Products) and APMA (Seiko Chemical Products) are exemplified as such compounds (Non-Patent Documents 1 and 2). TIFF0007719880000003.tif50168

[0013] However, the diphenylamino group of the above antioxidants inhibits radical polymerization, making it practically difficult to carry out radical copolymerization with polymerizable unsaturated monomers (Patent Document 9).

[0014] Additionally, several methods have been disclosed for introducing diphenylamino structures into elastomeric polymers by modification reactions. For example, a method of hydroformylating the side chains of an elastomer having olefinic unsaturated groups and then introducing diphenylamino groups (Patent Document 10) and a method of adding maleic anhydride to a diene copolymer in the presence of a free radical generator and then introducing diphenylamino groups (Patent Document 11) are known. However, these methods require an additional modification step of introducing diphenylamino groups after producing the base copolymer, making them impractical in terms of production costs.

[0015] A technology has also been disclosed in which 4-aminodiphenylamine is used in combination during crosslinking to chemically bond an anti-aging component to the reactive site of the elastomeric copolymer main chain (Patent Document 12), but there is a concern that this may deteriorate the compression set resistance properties, limiting its use. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] Japanese Patent Application Publication No. 11-21411 [Patent Document 2] WO 2007 / 005458 A1 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-254579 [Patent Document 4] WO 2006 / 001299 A1 [Patent Document 5] Japanese Patent Application Laid-Open No. 2011-032390 [Patent Document 6] WO 2011 / 58918 A1 [Patent Document 7] JP 2015-227402 A [Patent Document 8] WO 2011 / 093443 A1 [Patent Document 9] Japanese Patent Application Laid-Open No. 2009-209268 [Patent Document 10] Japanese Patent Application Publication No. 4-264106 [Patent Document 11] Japanese Patent Application Publication No. 5-230132 [Patent Document 12] WO 2020 / 158132 A1 [Non-patent literature]

[0017] [Non-Patent Document 1] Rubber Chem. Technol., Vol. 46, p. 106 (1973) [Non-patent document 2] Rubber Chem. Technol., Vol. 52, p. 883 (1979) Summary of the Invention [Problem to be solved by the invention]

[0018] The present invention has been made in view of the above-mentioned problems, and has as its object to provide an acrylic elastomer copolymer that is stabilized against thermo-oxidative degradation. [Means for solving the problem]

[0019] The present invention relates to a compound of the general formula TIFF0007719880000004.tif29129 (where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group, A is a direct bond or a divalent organic group, B is a direct bond, an oxygen atom, a sulfur atom, a sulfoxide group or a sulfone group, and x is 0 or 1), an alkyl (meth)acrylate monomer and / or an alkoxyalkyl (meth)acrylate monomer, and a cross-linking site monomer. [Effects of the Invention]

[0020] The acrylic elastomer copolymer of the present invention contains an antioxidant component in its polymer side chain, and the copolymer itself is stabilized against thermal oxidative degradation, eliminating the need to add a phenolic antioxidant or an amine antioxidant during production and processing. This eliminates the steps of measuring, adding, and mixing the additives during production and processing, and also eliminates concerns about defects due to poor dispersion of the additives.

[0021] As mentioned above, since the acrylic elastomer copolymer of the present invention contains an antiaging component in the polymer chain, the process of inactivating peroxy radicals generated by thermal oxidative degradation can be considered an intramolecular reaction. In contrast, the process when a commonly used phenolic antioxidant or amine-based antioxidant is added externally is an intermolecular reaction. As a result, if the same level of thermal aging resistance is required, the amount of the antiaging component (copolymerizable antioxidant) used in the present invention can be reduced to 50% or less of the amount of the conventional phenolic antioxidant or amine-based antioxidant used.

[0022] Furthermore, when the acrylic elastomer copolymer of the present invention is produced by emulsion polymerization, the copolymer itself has an anti-oxidative degradation effect, which makes it possible to prevent deterioration of the polymer emulsion during storage.

[0023] Furthermore, in the hot air drying or extrusion drying process after the copolymer coagulation process, the acrylic elastomer copolymer itself has the ability to prevent thermal (oxidative) degradation, thereby preventing its deterioration and enabling long-term storage in air thereafter.In other words, since it is stabilized against thermal or thermal oxidative degradation caused by the thermal history during the production process and storage stage, it is effective in improving its productivity and storage stability.

[0024] Furthermore, when an acrylic elastomer molded part obtained by crosslinking the acrylic elastomer copolymer of the present invention is used, the anti-aging component is chemically bonded to the rubber molecules, which prevents the anti-aging component from volatilizing into the air or being extracted by liquid media such as oils and fats or organic solvents. As a result, the life of the acrylic elastomer molded part can be extended even in a variety of deterioration environments.

[0025] The elastomeric copolymer of the present invention, in which a copolymerizable antioxidant has been copolymerized, can be blended with an elastomeric copolymer that does not contain any antioxidant or in which the antiaging component is not chemically bonded to the polymer chain, i.e., an elastomeric copolymer that is not stabilized against thermooxidative degradation, to impart antiaging properties to the crosslinked product, and is therefore expected to function as a polymeric antioxidant. [Brief explanation of the drawings]

[0026] [Figure 1] The change over time in the rate of change in strength at break of a cross-linked acrylic rubber at 190°C is shown graphically (Example 5: -●-, Example 6: -◆-, Comparative Example 1--●--, Comparative Example 2: --◆--; common to Figures 1 to 4). [Figure 2] This is a diagram showing the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber at 190°C. [Figure 3] This is a diagram showing the change over time in the rate of change in strength at break of a cross-linked acrylic rubber at 175°C. [Figure 4] This is a diagram showing the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber at 175°C. [Figure 5] For Examples 5 to 8 and Comparative Examples 1 and 2, the percentage change in strength at break after an air heating aging test in air (190°C, 200 hours) (white bars) is compared with the percentage change in strength at break when the same air heating aging test (190°C, 200 hours) was further conducted after immersion in IRM903 oil (black bars). [Figure 6]For Examples 5 to 8 and Comparative Examples 1 and 2, the percentage change in elongation at break after an air heating aging test in air (190°C, 200 hours) (white bars) is compared with the percentage change in elongation at break when the same air heating aging test (190°C, 200 hours) was further conducted after immersion in IRM903 oil (black bars). [Figure 7] 7 shows a diagram illustrating the change over time in the rate of change in strength at break of a cross-linked acrylic rubber at 190° C. (Example 10: --●-, Comparative Example 3: --▲--, Comparative Example 4: --◆--; common to FIGS. 7 and 8). [Figure 8] This is a diagram showing the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber at 190°C. [Figure 9] For Example 10 and Comparative Examples 3 and 4, the percentage change in strength at break after an air heating aging test in air (190°C, 200 hours) (white bars) is compared with the percentage change in strength at break when the same air heating aging test (190°C, 200 hours) was further conducted after immersion in IRM903 oil (black bars). [Figure 10] For Example 10 and Comparative Examples 3 and 4, the percentage change in elongation at break after an air heating aging test in air (190°C, 200 hours) (white bars) is compared with the percentage change in elongation at break when the same air heating aging test (190°C, 200 hours) was further conducted after immersion in IRM903 oil (black bars). [Figure 11] For Example 10 and Comparative Examples 3 and 4, the percentage change in strength at break after an air heating aging test in air (190°C, 300 hours) (white bars) is compared with the percentage change in strength at break when a combined test consisting of air heating (175°C, 150 hours), IRM903 oil immersion, and air heating (190°C, 300 hours) was conducted (black bars). [Figure 12] For Example 10 and Comparative Examples 3 and 4, the percentage change in elongation at break after an air heating aging test in air (190°C, 300 hours) (white bars) is compared with the percentage change in elongation at break when a combined test consisting of air heating (175°C, 150 hours), IRM903 oil immersion, and air heating (190°C, 300 hours) was conducted (black bars). [Figure 13]The change over time in the rate of change in strength at break of an acrylic rubber cross-linked product at 190°C is shown graphically (Example 12: --●-, Comparative Example 5: --●--, Comparative Example 6--▲--, Comparative Example 7--◆--; common to Figures 13 to 14). [Figure 14] This is a diagram showing the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber at 190°C. [Figure 15] 15A and 15B are diagrams showing the change over time in the rate of change in strength at break of a cross-linked acrylic rubber at 175° C. (Example 14: --●-, Comparative Example 8: --▲--, Comparative Example 9: --◆--; common to FIGS. 15 and 16). [Figure 16] This is a diagram showing the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber at 175°C. [Figure 17] 17A and 17B are diagrams showing the change over time in the rate of change in strength at break of a cross-linked acrylic rubber at 175° C. (Example 15: --●-, Comparative Example 10: --▲--, Comparative Example 11: --◆--; common to FIGS. 17 and 18). [Figure 18] This is a diagram showing the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber at 175°C. [Figure 19] For Examples 18 and 19 and Comparative Example 12, the percentage change in elongation at break after an air heating aging test (175°C, 300 hours) (white bars) is compared with the percentage change in elongation at break after a combined test consisting of IRM903 oil immersion (150°C, 168 hours) and air heating (175°C, 300 hours) (black bars). [Figure 20] For Examples 25 to 27 and Comparative Examples 13 to 15, the percentage change in strength at break after an air heating aging test (190°C, 200 hours) (white bars) is compared with the percentage change in strength at break after a combined test consisting of IRM903 oil immersion (150°C, 168 hours) and air heating (190°C, 200 hours) (black bars). [Figure 21] For Examples 25 to 27 and Comparative Examples 13 to 15, the percentage change in elongation at break after an air heating aging test (190°C, 200 hours) (white bars) is compared with the percentage change in elongation at break after a combined test consisting of IRM903 oil immersion (150°C, 168 hours) and air heating (190°C, 200 hours) (black bars). DETAILED DESCRIPTION OF THE INVENTION

[0027] The copolymerizable antioxidant used in the present invention is synthesized using diphenylamine, 4-aminodiphenylamine, phenothiazine or its 5,5-dioxide, 2-acetylphenothiazine, etc. as a starting material, and is a compound having a diphenylamine structure as a basic skeleton in which the hydrogen atom on the amino group is substituted with an alkyl group, an aralkyl group, or an acyl group, and having a polymerizable unsaturated group, and is represented by general formula [I]. Here, (meth)acrylate refers to acrylate or methacrylate.

[0028] Specifically, the compound represented by the following general formula [I] is used. TIFF0007719880000005.tif29129 where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group; A is a direct bond or a divalent organic group; B is a direct bond, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group; and x is 0 or 1.

[0029] Specific examples of aliphatic hydrocarbon groups having 1 to 20 carbon atoms example Examples of the alkyl group include primary hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-undecyl, n-pentadecyl, n-heptadecyl, and n-octadecyl groups; secondary hydrocarbon groups such as an isopropyl group, a 2-butyl group, a 2-pentyl group, a 3-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-heptyl group, a 3-heptyl group, a 4-heptyl group, a 2-octyl group, a 3-octyl group, and a 4-octyl group; tertiary hydrocarbon groups such as a tertiary butyl group, a 1,1-dimethyl-1-propyl group, a 1,1-dimethyl-1-butyl group, a 1,1-dimethyl-1-pentyl group, a 1,1-dimethyl-1-hexyl group, a 3-methyl-3-pentyl group, a 3-ethyl-3-pentyl group, and a 3-methyl-3-hexyl group; alicyclic hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-methyl-1-cyclopentyl group, and a 1-methyl-1-cyclohexyl group; Examples include a 1-adamantyl group.

[0030] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a 1-phenylethyl group.

[0031] The acyl group having 2 to 20 carbon atoms is represented by the following general formula. TIFF0007719880000006.tif15129 where, R 3 is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or an aromatic hydrocarbon group having 6 to 19 carbon atoms, and the aliphatic hydrocarbon group having 1 to 19 carbon atoms is R excluding those having 20 carbon atoms. 1 Examples of the aromatic hydrocarbon group having 6 to 19 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group.

[0032] A is a direct bond or a divalent organic group, and the divalent organic group is not particularly limited as long as it does not inhibit the polymerization reaction. A is preferably a direct bond or a group -(CH2) n O(C=O)-(n: 1 to 5) or group -NH(C=O)(CH2) n O(C=O)-(n: 1 to 5).

[0033] When x is 0, the copolymerizable antioxidant is represented by the following general formula [II]: TIFF0007719880000007.tif21129Specific examples include: An example is TIFF0007719880000008.tif54166.

[0034] When x is 1, the copolymerizable antioxidant is represented by the following general formula [III]: TIFF0007719880000009.tif25129As a specific example, Examples include TIFF0007719880000010.tif106166, TIFF0007719880000011.tif78166, and TIFF0007719880000012.tif56166.

[0035] When copolymerizing a copolymerizable antioxidant with a polymerizable unsaturated monomer, the copolymerizable antioxidant [I] is used in an amount of about 0.005 to 5 parts by weight, preferably about 0.01 to 3 parts by weight, per 100 parts by weight of the monomer mixture. The molar fraction of the copolymerizable antioxidant in the copolymer is about 0.002 to 2 mol%, preferably about 0.004 to 1 mol%. If used in a proportion less than this, sufficient antiaging effect cannot be expected, while if used in a proportion greater than this, no improvement in antiaging effect can be expected, making it uneconomical.

[0036] The alkyl(meth)acrylate monomer and / or alkoxyalkyl(meth)acrylate monomer constituting the acrylic elastomer copolymer of the present invention is at least one (meth)acrylate selected from alkyl(meth)acrylates having an alkyl group with 1 to 20 carbon atoms, aralkyl(meth)acrylates having an aralkyl group with 7 to 20 carbon atoms, and alkoxyalkyl(meth)acrylates having an alkoxyalkyl group with 2 to 20 carbon atoms.

[0037] Examples of alkyl(meth)acrylates that can be used include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, cyclohexyl(meth)acrylate, n-decyl(meth)acrylate, n-dodecyl(meth)acrylate, and n-octadecyl(meth)acrylate.

[0038] As the aralkyl(meth)acrylate, for example, benzyl(meth)acrylate is used.

[0039] Examples of alkoxyalkyl (meth)acrylates that can be used include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, and polypropylene glycol monoethyl ether (meth)acrylate.

[0040] As the crosslinking site monomer constituting the acrylic elastomer copolymer of the present invention, an α,β-unsaturated carboxylic acid monomer, an active chlorine-containing unsaturated monomer or an epoxy group-containing unsaturated monomer is used.

[0041] The α,β-unsaturated carboxylic acid monomer may be a monobasic α,β-unsaturated carboxylic acid, a dibasic α,β-unsaturated carboxylic acid, or a dibasic α,β-unsaturated carboxylic acid monoalkyl ester.

[0042] Examples of the monobasic α,β-unsaturated carboxylic acid include acrylic acid and methacrylic acid.

[0043] Examples of the dibasic α,β-unsaturated carboxylic acid include maleic acid, fumaric acid, itaconic acid, and citraconic acid.

[0044] Examples of dibasic α,β-unsaturated carboxylic acid monoalkyl esters include monoalkyl esters of maleic acid, fumaric acid, itaconic acid, and citraconic acid. Specific examples include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, mono-n-butyl maleate, monoisobutyl maleate, mono-n-hexyl maleate, monocyclohexyl maleate, monomethyl fumarate, monoethyl fumarate, mono-n-propyl fumarate, monoisopropyl fumarate, mono-n-butyl fumarate, monoisobutyl fumarate, mono-n-hexyl fumarate, and monocyclohexyl fumarate.

[0045] Examples of the active chlorine-containing unsaturated monomer include 4-chloromethylstyrene and vinyl chloroacetate.

[0046] Examples of the epoxy group-containing unsaturated monomer include glycidyl acrylate and glycidyl methacrylate.

[0047] The crosslinking site monomer in the acrylic elastomer copolymer of the present invention is copolymerized in a proportion of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.

[0048] In addition to these main components of the acrylic elastomer copolymer of the present invention, other polymerizable unsaturated monomers can be used as needed.

[0049] Examples of the polymerizable unsaturated monomer include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, acrylonitrile, methacrylonitrile, acrylic acid amide, vinyl acetate, methyl vinyl ether, ethyl vinyl ether, ethylene, propylene, piperylene, butadiene, isoprene, chloroprene, cyclopentadiene, vinyl chloride, and vinylidene chloride.

[0050] The acrylic elastomer copolymer can be produced by a general copolymerization method for acrylic rubber, which can be carried out by any method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.

[0051] For example, when emulsion polymerization or suspension polymerization is used, the reaction is carried out at a reaction temperature of about -10 to 100°C, preferably about 5 to 80°C.

[0052] As the polymerization initiator for the reaction, organic peroxides or organic hydroperoxides such as benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, and p-methylene hydroperoxide, diazo compounds such as azobisisobutyronitrile and azobisisobutylamidine, and peroxide salts such as ammonium salts typified by ammonium persulfate, sodium salts, and potassium salts may be used alone or as a redox system.

[0053] A particularly preferred emulsifier for use in emulsion polymerization is an aqueous solution of an anionic or nonionic surfactant, the pH of which is adjusted with an acid or base as necessary, and which is buffered with an inorganic salt.

[0054] The polymerization reaction is continued until the conversion rate of the monomer mixture reaches 90% or more. The obtained aqueous latex is coagulated by a salt-acid coagulation method, a method using salts such as calcium chloride, magnesium sulfate, sodium sulfate, or ammonium sulfate, a method using boron compounds such as boric acid or borax, a thermal coagulation method, or a freeze coagulation method, and the obtained copolymer is thoroughly washed with water and dried. This acrylic rubber has a Mooney viscosity ML of about 5 to 100, preferably about 20 to 80. 1+4 (100°C).

[0055] The copolymerizable antioxidant [I] can be copolymerized with polymerizable unsaturated monomers other than alkyl (meth)acrylate monomers and / or alkoxyalkyl (meth)acrylate monomers, and can be used to produce elastomeric copolymers such as styrene-butadiene rubber (SBR), chloroprene rubber (CR), ethylene-vinyl acetate rubber (EVA), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), ethylene-methyl acrylate rubber (AEM), etc. The polymerization reaction is preferably radical polymerization or anionic polymerization.

[0056] The elastomer copolymer of the present invention can be crosslinked with a crosslinking agent depending on the type of crosslinking site monomer used to form a crosslinkable acrylic elastomer copolymer.

[0057] Here, for example, when the crosslinking site monomer is an α,β-unsaturated carboxylic acid monomer, a polyamine compound is used as the crosslinking agent.

[0058] Polyvalent amine crosslinking agents include hexamethylenediamine, hexamethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexanediamine, 4,4'-bis(aminocyclohexyl)methane, ethylenediamine, ethylenediamine carbamate, cyclohexanediamine, hexamethylenediamine benzoate, diamino-modified siloxane, 4,4'-methylenebiscyclohexylamine, bis(4-amino-3-methyldicyclohexyl)methane, 4,4'-methylenebiscyclohexylamine-cinnamaldehyde adduct, 4,4′-(α,α-Dimethylbenzyl)diphenylamine, 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, p-phenylenediamine, p,p′-ethylenedianiline, 4,4′-(p-phenylenediisopropylidene)dianiline, 4,4′-(m-phenylenediisopropylidene)dianiline, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenol, bis[4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, m-xylylenediamine, p-xylylenediamine, and the like.

[0059] When crosslinking with a polyamine compound, a guanidine compound, a diazabicycloalkene compound or an organic acid salt thereof is used as a crosslinking accelerator.

[0060] Examples of the guanidine compound include tetramethylguanidine, tetraethylguanidine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, etc. Preferred are 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, or a combination thereof.

[0061] The diazabicycloalkene compound is preferably 1,8-diazabicyclo[5.4.0]-7-undecene.

[0062] The organic acid salt of the diazabicycloalkene compound is preferably an organic acid salt of 1,8-diazabicyclo[5.4.0]-7-undecene.

[0063] The organic acid used for the organic acid salt of 1,8-diazabicyclo[5.4.0]-7-undecene includes an organic monobasic acid or an organic dibasic acid.

[0064] Examples of organic monobasic acids include n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, n-capric acid, n-lauric acid, p-toluenesulfonic acid, phenol, etc. Examples of organic dibasic acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, orthophthalic acid, phthalic acid, etc., and monocarboxylic or dicarboxylic acids having 6 to 18 carbon atoms are preferred.

[0065] When the crosslinking site monomer is an unsaturated monomer containing active chlorine, a triazine thiol compound or an alkali metal salt of a fatty acid is used as the crosslinking agent.

[0066] Examples of triazine thiol compounds include triazine thiol (2,4,6-trimercapto-s-triazine) and its derivatives. Examples of derivatives include compounds in which part of the thiol group of triazine thiol is substituted with an amino group or an aliphatic hydrocarbon group. 2,4,6-trimercapto-s-triazine is preferred.

[0067] When the crosslinking agent is a triazine thiol compound, the crosslinking accelerator can preferably be a metal dithiocarbamate or thiuram sulfide, etc. Examples of the metal dithiocarbamate include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc di-n-hexyldithiocarbamate, zinc di-n-octyldithiocarbamate, zinc di-n-decyldithiocarbamate, zinc di-n-dodecyldithiocarbamate, zinc methylbenzyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc methylcyclohexyldithiocarbamate, and zinc dicyclohexyldithiocarbamate. Specific examples of thiuram sulfides include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram tetrasulfide.

[0068] Examples of the fatty acid alkali metal salts include alkali metal salts of fatty acids having 10 to 22 carbon atoms. Sodium stearate and potassium stearate are particularly preferred.

[0069] Furthermore, when a fatty acid alkali metal salt is used as a crosslinking agent, the crosslinking reaction can be effectively promoted by using sulfur in combination, and therefore the crosslinking method using a fatty acid alkali metal salt in combination with sulfur is more common.

[0070] When the crosslinking site unsaturated monomer is an epoxy group-containing unsaturated monomer, an aromatic carboxylic acid ammonium salt or a polyamine compound used when the crosslinking site monomer is an α,β-unsaturated carboxylic acid monomer is used as the crosslinking agent. Examples of the aromatic carboxylic acid ammonium salt include ammonium benzoate.

[0071] Examples of the crosslinking accelerator used when the crosslinking site monomer is an epoxy group-containing unsaturated monomer include the crosslinking accelerators used when the crosslinking site monomer is an α,β-unsaturated carboxylic acid monomer, imidazole compounds, quaternary ammonium salts, tertiary amine compounds, and alkali metal salts of aliphatic carboxylic acids.

[0072] Examples of imidazole compounds include 2-methylimidazole and 2-phenylimidazole. Examples of quaternary ammonium salts include tetra-n-butylammonium bromide and octadecyltri-n-butylammonium bromide. Examples of tertiary amine compounds include dimethylstearylamine. Examples of alkali metal salts of aliphatic carboxylic acids include sodium stearate and potassium stearate.

[0073] Crosslinking is carried out by primary crosslinking at about 120 to 250°C for about 1 to 60 minutes, and if necessary, oven crosslinking (secondary crosslinking) at about 120 to 200°C for about 1 to 20 hours. [Example]

[0074] The present invention will now be described in detail with reference to examples, although the present invention, including its effects, is not limited to these examples.

[0075] Reference example 1 Preparation of compound (a) TIFF0007719880000013.tif37129Compound (a) was produced by the following method. TIFF0007719880000014.tif47167

[0076] [1st step] (a-1)→(a-2): A 1000 mL three-neck flask equipped with a magnetic stirrer, thermometer, and dropping funnel was charged with 36.0 g (359 mmol) of succinic anhydride, 30 g of N,N-dimethylacetamide, and 90 g of toluene. A solution of 63.0 g (342 mmol) of 4-aminodiphenylamine in 120 g of toluene was added dropwise to this solution at room temperature over 1 hour, and the reaction was continued for an additional 0.5 hours. After the reaction was complete, 600 mL of toluene was added to the reaction mixture, and the resulting solid was filtered to obtain 87.1 g (90% crude yield) of a crude product as a brown solid. The resulting crude product was a mixture of two components, with carboxylic acid compound (a-2) being the main component. TIFF0007719880000015.tif25129

[0077] [Second step] (a-2)→(a-3): In a 2000 ml three-neck flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser, 113.2 g (approximately 398 mmol) of the carboxylic acid compound mixture obtained in the first step, 4.8 g of concentrated sulfuric acid, 96 g of methanol, and 1 L of toluene were placed and reacted at 70°C for 2 hours. After the reaction was completed, water and toluene were distilled off from the reaction mixture under reduced pressure, and the residue was dissolved in methyl isobutyl ketone. This was washed twice with a 1 wt% aqueous solution of sodium bicarbonate, and the organic layer was treated with anhydrous magnesium sulfate and synthetic aluminum silicate (Kyowa Chemical Industry Co., Ltd.) as an alkali adsorbent. Kyoward 700) and activated carbon (Shirasagi A, a product of Osaka Gas Chemicals) were added. After filtering off the insoluble matter, the volatile components were distilled off from the organic layer under reduced pressure to obtain 115.5 g of a crude product (crude yield 97%) as a pale red solid. The crude product obtained was recrystallized three times using toluene containing Kyoward 700, to obtain 62.6 g of carboxylic acid methyl ester (a-3) (yield 53%) as a colorless solid. TIFF0007719880000016.tif29129 1 H NMR (300MHz, Acetone-d6, δ ppm): 2.65 (s, 4H, -NHC(=O)C H 2C H 2C(=O)OCH3) 3.63(s, 3H, -NHC(=O)CH2CH2C(=O)OC H 3) 6.79 (t, 1H, J=7.2Hz, Ar) 7.00-7.25 (m, 6H, Ar) 7.26 (brs, 1H, -N H C(=O)CH2CH2C(=O)OCH3) 7.54 (d, 2H, J=9.0Hz, Ar) 9.05 (brs, 1H, ArN H Ar)

[0078] [3rd step] (a-3)→(a-4): A 300 mL three-neck flask equipped with a magnetic stirrer, thermometer, and dropping funnel was charged with 40 g (134 mmol) of the carboxylic acid methyl ester (a-3) obtained in the second step, 17.8 g of pyridine, and 200 mL of dichloromethane. The contents were cooled to 5°C. While maintaining the internal temperature at 5-20°C, 13.8 g (176 mmol) of acetyl chloride was added dropwise, and the reaction was continued for an additional 1 hour. After the reaction was completed, the mixture was diluted with 100 mL of dichloromethane and washed three times with saturated aqueous sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were then removed from the filtrate by distillation under reduced pressure to obtain 51.9 g of the crude product. This product was recrystallized using a 3:1 ethyl acetate / n-hexane mixed solvent to obtain 43.0 g (94% yield) of the N-acetylated methyl ester (a-4) as a colorless solid. TIFF0007719880000017.tif31129 1 H NMR (300MHz, Chloroform-d, δ ppm): 2.06 (s, 3H, NC(=O)C H 3) 2.64 (t, J=6.3Hz, 2H, -NHC(=O)C H 2CH2C(=O)OCH3) 2.74 (t, J=6.3Hz, 2H, -NHC(=O)CH2C H 2C(=O)OCH3) 3.71(s, 3H, -NHC(=O)CH2CH2C(=O)OC H 3) 7.1-7.6 (m, 9H, Ar) 7.84 (brs, 1H, -N H C(=O)CH2CH2C(=O)OCH3)

[0079] [4th step] (a-4)→(a-5): A 1000 mL four-neck flask equipped with a magnetic stirrer, thermometer, gas outlet, and reflux condenser was charged with 30 g (88.1 mmol) of the N-acetylated methyl ester compound (a-4) obtained in the third step and 150 mL of methanol, and the contents were heated to 45°C. While maintaining the internal temperature at 45-55°C, 10 g (264 mmol) of sodium borohydride was slowly added and the reaction continued for an additional hour. The methanol was removed by distillation under reduced pressure, and the residue was dissolved in methyl isobutyl ketone. The organic layer was washed twice with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. The insoluble matter was filtered off. Volatile components were removed by distillation under reduced pressure from the filtrate, yielding 26.7 g (97% crude yield) of terminal alcohol compound (a-5) as a colorless solid. Recrystallization was carried out using a 5 / 2 volume ethyl acetate / ethanol mixed solvent to yield 20.0 g (73% yield) of terminal alcohol compound (a-5) as a colorless solid. TIFF0007719880000018.tif32129 1 H NMR (300MHz, Chloroform-d, δ ppm): 1.91 (quin, J=6.3Hz, 2H, -C(=O)CH2C H 2CH2OH) 2.06 (s, 3H, NC(=O)C H 3) 2.47 (t, J=6.6Hz, 2H, -C(=O)C H 2CH2CH2O-) 2.65 (brs, 1H, -C(=O)CH2CH2CH2O H ) 3.69 (t, J=6.0Hz, 2H, -C(=O)CH2CH2C H 2O-) 7.1-7.6 (m, 9H, Ar)

[0080] [5th step] (a-5)→(a): A 500 mL three-neck flask equipped with a magnetic stirrer, thermometer, and dropping funnel was charged with 37.8 g (121 mmol) of the terminal alcohol compound (a-5) obtained in Step 4, 200 mL of dichloromethane, and 16.1 g of pyridine, and the contents were cooled to 5°C. While maintaining the internal temperature at 5-15°C, 16.4 g (157 mmol) of methacryloyl chloride was added dropwise, and the reaction was continued for an additional hour. The contents were diluted with 100 mL of dichloromethane and washed three times with saturated aqueous sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. 200 ppm of 4-methoxyphenol relative to the product was added to the filtrate. Volatile components were removed by distillation under reduced pressure, yielding 53.0 g of crude methacrylate (a) (crude yield 115%). The crude methacrylate was subjected to column chromatography (carrier: Wakogel C300) using ethyl acetate as an eluent to obtain 42.1 g (yield 92%) of methacrylate (a) as a colorless viscous liquid. TIFF0007719880000019.tif37129 1 H NMR (300MHz, Cloroform-d, δ ppm): 1.93 (t, J=1.2Hz, 3H, CH2=CC H 3) 2.06 (s, 3H, NC(=O)C H 3) 2.09 (quin, J=6.6Hz, 2H, -C(=O)CH2C H 2CH2O-) 2.41 (t, J=7.2Hz, 2H, -C(=O)C H 2CH2CH2O-) 4.23 (t, J=6.0Hz, 2H, -C(=O)CH2CH2C H 2O-) 5.56 (t, J=1.5Hz, 1H, -C(=O)-C=C- H (trans to the carbonyl group) 6.11 (s, 1H, -C(=O)-C=C-H (cis to the carbonyl group) 6.1-7.8 (m, 9H, Ar) 8.00 (brs, 1H, N H)

[0081] Reference example 2 Preparation of compound (b) TIFF0007719880000020.tif29129Compound (b) was produced by the following method. TIFF0007719880000021.tif74166

[0082] [1st process] [PTZ] → (b-1): A 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, dropping funnel, nitrogen gas inlet, and outlet tube was charged with 40.0 g (201 mmol) of phenothiazine (PTZ) and 200 ml of N,N-dimethylformamide. The system was cooled to below 5°C under a nitrogen atmosphere. While maintaining the system temperature below 10°C, 7.2 g (300 mmol) of sodium hydride was added and the reaction was allowed to proceed for 1 hour. While maintaining the system temperature below 20°C, 34.2 g (241 mmol) of iodomethane was added dropwise, and the reaction was allowed to proceed for an additional hour. After the reaction was complete, the reaction mixture was added to saturated aqueous sodium chloride solution. The precipitated colorless solid was filtered and dissolved in ethyl acetate. After washing with saturated aqueous sodium chloride solution, the organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered. Volatile components were removed from the filtrate by distillation under reduced pressure, yielding 45.9 g of crude product (crude yield 107%). Recrystallization from ethanol gave 40.5 g (yield 94%) of 10-methyl-10H-phenothiazine (b-1) as colorless needle crystals. TIFF0007719880000022.tif25129 1 H NMR (400MHz, Acetone-d6, δ ppm): 3.39 (s, 3H, NC H 3) 6.91-6.98 (m, 4H, Ar) 7.14 (dd, J=7.6Hz, J=1.6Hz, 2H, Ar) 7.21 (td, J=7.6Hz, J=1.6Hz, 2H, Ar)

[0083] [Second process] (b-1)→(b-2): A 500 ml four-neck flask equipped with a magnetic stirrer, dropping funnel, thermometer, gas inlet / outlet, and reflux condenser was charged with 210 ml of N,N-dimethylformamide. Under a nitrogen atmosphere, 129.4 g (844 mmol) of phosphoryl chloride was added dropwise while maintaining the internal temperature of the system below 10°C, and the reaction was continued for an additional 30 minutes. Next, 30 g (141 mmol) of N-methyl-10H-phenothiazine (b-1) obtained in the first step above was added, and the reaction was continued at 60°C for 24 hours. After the reaction was completed, the contents were poured into an aqueous sodium acetate solution and neutralized with sodium bicarbonate. The product was extracted from the resulting aqueous solution with ethyl acetate, and the organic layer was washed once with saturated aqueous sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, and after filtering off insoluble matter, the volatile components were removed from the filtrate by distillation under reduced pressure, yielding 33.5 g of crude product as a red oil (crude yield 98%). The crude product was purified by column chromatography (Wakogel C300) using ethyl acetate as an eluent to remove low Rf components, yielding 33.2 g (98% yield) of the desired crude product as a yellow solid. Further recrystallization using ethyl acetate afforded 30.1 g (88% yield) of 10-methyl-10H-phenothiazine-3-carbaldehyde (b-2) as a yellow crystal. TIFF0007719880000023.tif29129 1 H NMR (400MHz, Acetone d6, δ ppm): 3.49 (s, 3H, NC H 3) 7.00-7.06 (m, 2H, Ar) 7.10 (d, J=8.4Hz, 1H, Ar) 7.15-7.19 (m, 1H, Ar) 7.22-7.28(m, 1H, Ar) 7.61(d, J=1.6Hz, 1H, Ar) 7.75(dd, J=8.4Hz, J=1.6Hz, 1H, Ar) 9.85(s, 1H, -C H O)

[0084] [3rd step] (b-2) → (b-3): A 2000 ml four-neck flask equipped with a magnetic stirrer, thermometer, gas outlet, and reflux condenser was charged with 30 g (124 mmol) of compound (b-2) obtained in the second step and 1200 ml of methanol. While maintaining the internal temperature below 30°C, 4.7 g (124 mmol) of sodium borohydride was slowly added and the reaction was continued for an additional hour. The methanol was removed by distillation under reduced pressure, and the residue was dissolved in methyl isobutyl ketone. The organic layer was washed once with saturated aqueous sodium chloride solution. The washed organic layer was then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure, yielding 29.4 g (97% crude yield) of the crude product as a pale yellow solid. The product was recrystallized using ethyl acetate to yield 28.2 g (93% yield) of 3-hydroxymethyl-10-methyl-10H-phenothiazine (b-3) as a pale yellow solid. TIFF0007719880000024.tif25129 1 H NMR (400MHz, Acetone d6, δ ppm): 3.38 (s, 3H, NC H 3) 4.08 (t, J=6.0Hz, 1H, -CH2O H ) 4.53 (d, J=6.0Hz, 2H, -C H 2OH) 6.87-6.98 (m, 3H, Ar) 7.10-7.23 (m, 4H, Ar)

[0085] [4th step] (b-3) → (b-4): Into a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser, 17.0 g (70 mmol) of compound (b-3) obtained in the third step, 150 ml of acetic acid, and 19.0 g (168 mmol) of 30 wt % hydrogen peroxide solution were placed, and the mixture was reacted at 60° C. for 1 hour and then at 80° C. for 1 hour. The acetic acid was distilled off from the reaction mixture under reduced pressure, and the residue was recrystallized using methanol to obtain 17.8 g (yield 92%) of 3-hydroxymethyl-10-methyl-10H-phenothiazine-5,5-dioxide (b-4) as a pale yellow solid. TIFF0007719880000025.tif29129 1 H NMR (400MHz, Acetone d6, δ ppm): 3.80 (s, 3H, -NC H 3) 4.43 (t, J=6.0Hz, 1H, -CH2O H ) 4.75 (d, J=6.0Hz, 2H, -C H 2OH) 7.35 (t, J=7.6Hz, 1H, Ar) 7.56 (t, J=8.4Hz, 2H, Ar) 7.68-7.76 (m, 2H, Ar) 8.00-8.05 (m, 2H, Ar)

[0086] [5th step] (b-4) → (b-5): A 500 mL four-neck flask equipped with a magnetic stirrer, thermometer, dropping funnel, gas inlet, and outlet tube was charged with 15.3 g (121 mmol) of oxalyl chloride and 225 mL of dichloromethane. The mixture was cooled to -80 to -70 °C under a nitrogen atmosphere. 14.1 g (181 mmol) of dimethyl sulfoxide was slowly added dropwise, and the mixture was allowed to react for an additional 30 minutes. Next, 16.5 g (60 mmol) of compound (b-4), previously dissolved in 8 g of dimethyl sulfoxide, was added dropwise, and the mixture was allowed to react for an additional 2 hours at -80 to -70 °C. 36.6 g of triethylamine was then added, and the mixture was allowed to warm to room temperature. A saturated aqueous solution of sodium chloride was added to the reaction mixture, and the product was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were removed from the filtrate by distillation under reduced pressure, yielding 28.0 g of crude product (crude yield 94%). The crude product was subjected to column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent to obtain 15.4 g (yield 94%) of compound (b-5) as a pale yellow solid. TIFF0007719880000026.tif29129 1 H NMR (400MHz, CDCl3, δ ppm): 3.79 (s, 3H, NC H 3) 7.35-7.45 (m, 3H, Ar) 7.66-7.73 (m, 1H, Ar) 8.11-8.16 (m, 2H, Ar) 8.58 (d, J=1.6Hz, 1H, Ar) 10.00 (s, 1H, -C H O)

[0087] [6th step] (b-5)→(b): 250 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, gas inlet tube, and gas outlet tube. The reaction vessel was cooled to below 10°C while purging with nitrogen. 11.2 g (99.7 mmol) of potassium tert-butoxide was added, followed by 35.6 g (99.7 mmol) of methyltriphenylphosphonium bromide, and the reaction was carried out for 30 minutes. 22.7 g (83.1 mmol) of compound (b-5) was added to the reaction mixture and the reaction was carried out for 2 hours at 10-30°C. The resulting reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. After drying over anhydrous magnesium sulfate, insoluble matter was filtered off, and the volatile components were removed from the filtrate under reduced pressure, yielding 47.5 g of residue. The residue was subjected to column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent to remove triphenylphosphine oxide, and then recrystallized using acetone to obtain 8.8 g (yield 39%) of compound (b) as a colorless solid. TIFF0007719880000027.tif29129 1 H NMR (400MHz, CDCl3, δ ppm): 3.71 (s, 3H, NC H 3) 5.31 (d, J=11.2Hz, 1H, C H 2 = CH-Ar (trans to the Ar group) 5.79 (d, J=17.6Hz, 1H, C H 2 = CH-Ar (cis to Ar group) 6.74 (dd, J=11.2Hz, 17.6Hz, 1H, CH2=C H -Ar) 7.23-7.34 (m, 3H, Ar) 7.59-7.69 (m, 2H, Ar) 8.09-8.15 (m, 2H, Ar)

[0088] Reference example 3 Preparation of compound (c) TIFF0007719880000028.tif27129Compound (c) was produced by the following method. TIFF0007719880000029.tif72166

[0089] [1st process] [PTZ] → (c-1): Using 38.7 g (194 mmol) of phenothiazine [PTZ], 7.0 g (292 mmol) of sodium hydride, 28.6 g (233 mmol) of 1-bromopropane, and 200 ml of N,N-dimethylformamide, a reaction similar to that in Step 1 of Reference Example 1 was carried out. The resulting crude product was recrystallized using ethanol to obtain 42.1 g (yield 90%) of compound (c-1) as a colorless solid. TIFF0007719880000030.tif23129 1 H NMR (400MHz, Acetone-d6, δ ppm): 0.98 (t, J=7.2Hz, 3H, -CH2CH2C H 3) 1.79 (sext, J=7.2Hz, 2H, -CH2C H 2CH3) 3.90 (t, J=7.2Hz, 2H, -C H 2CH2CH3) 6.93 (td, J=7.6, 1.2Hz, 2H, Ar) 7.00 (d, J=8.0Hz, 2H, Ar) 7.13 (dd, J=7.6Hz, 1.6Hz, 2H, Ar) 7.16-7.22 (m, 2H, Ar)

[0090] [Second process] (c-1)→(c-2): A reaction similar to that in the second step of Reference Example 1 was carried out using 34 g (141 mmol) of compound (c-1), 129.4 g (844 mmol) of phosphorus oxytrichloride, and 210 ml of N,N-dimethylformamide, to obtain 35.8 g (yield 94%) of compound (c-2). TIFF0007719880000031.tif27129 1 H NMR (400MHz, Acetone-d6) δppm (TMS) 1.01 (t, J=7.2Hz, 3H, NCH2CH2C H 3) 1.83 (sext, J=7.2Hz, 2H, NCH2C H 2CH3) 3.99 (t, J=7.2Hz, 2H, NC H 2CH2CH3) 7.01 (td, J=8.0Hz, 1.2Hz, 1H, Ar) 7.08 (d, J=7.6Hz, 1H, Ar) 7.12-7.18 (m, 2H, Ar) 7.20-7.26 (m, 1H, Ar) 7.60 (d, J=2.4Hz, 1H, Ar) 7.73 (dd, J=8.4Hz, 2.0Hz, 1H, Ar) 9.83 (s, 1H, -C H O)

[0091] [3rd step] (c-2)→(c-3): As in the third step of Reference Example 1, 35.8 g (133 mmol) of compound (c-2), 5.0 g (133 mmol) of sodium borohydride, and 400 ml of tetrahydrofuran were used, and the reaction was carried out at 60°C for 2 hours to obtain 36.1 g (yield 100%) of compound (c-3). TIFF0007719880000032.tif23129

[0092] [4th step] (c-3)→(c-4): Similar to the fourth step of Reference Example 1, a reaction was carried out using 36.1 g (133 mmol) of compound (c-3), 45.6 g (402 mmol) of a 30 wt% aqueous hydrogen peroxide solution, and 200 ml of acetic acid to obtain 40.6 g (yield 100%) of compound (c-4). TIFF0007719880000033.tif27129

[0093] [5th step] (c-4)→(c-5): In the same manner as in the fifth step of Reference Example 1, a reaction was carried out using a solution of 40.6 g (134 mmol) of compound (c-4) dissolved in 50 g of dimethyl sulfoxide, 33.9 g (268 mmol) of oxalyl chloride, 31.4 g (402 mmol) of dimethyl sulfoxide, 300 ml of dichloromethane-acetic acid, and 81.2 g (804 mmol) of triethylamine, to obtain 40.6 g of compound (c-5) (yield 97%). TIFF0007719880000034.tif27129

[0094] [6th step] (c-5)→(c): Similar to the sixth step of Reference Example 1, a reaction was carried out using 39.2 g (130 mmol) of compound (c-5), 17.5 g (156 mmol) of potassium tert-butoxide, 55.7 g (156 mmol) of methyltriphenylphosphonium bromide, and 350 mL of tetrahydrofuran, yielding 73.9 g of crude product. The crude product was subjected to column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent to remove triphenylphosphine oxide, yielding 18.0 g (46% yield) of the target compound as a yellow solid. Further recrystallization using ethyl acetate yielded 16.3 g (42% yield) of compound (c). TIFF0007719880000035.tif27129 1 H NMR (400MHz, Chloroform-d) δppm (TMS) 1.07 (t, J=7.6Hz, 3H, NCH2CH2C H 3) 1.95 (sext, J=7.6Hz, 2H, NCH2C H 2CH3) 4.11 (t, J=7.6Hz, 2H, NC H 2CH2CH3) 5.30 (d, J=11.2Hz, 1H, C H 2 = CH-Ar (trans to the Ar group) 5.78 (d, J=17.6Hz, 1H, C H 2 = CH-Ar (cis to Ar group) 6.73 (dd, J=11.2Hz, 17.6Hz, 1H, CH2=C H -Ar) 7.23-7.35 (m, 3H, Ar) 7.58-7.68 (m, 2H, Ar) 8.10-8.16 (m, 2H, Ar)

[0095] Reference example 4 Compound (d) was produced by the following method. TIFF0007719880000036.tif76166

[0096] [1st step] [AcPTZ] → (d-1): A 2000 mL four-neck flask equipped with a magnetic stirrer, thermometer, gas outlet, and reflux condenser was charged with 25.0 g (104 mmol) of 2-acetylphenothiazine [AcPTZ] (a product of Tokyo Chemical Industry Co., Ltd.) and 1000 mL of methanol. While maintaining the internal temperature at 45-55°C, 19.6 g (518 mmol) of sodium borohydride was slowly added and the reaction continued for an additional hour. The methanol was removed by distillation under reduced pressure, and the residue was dissolved in ethyl acetate. The organic layer was washed once with saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The insoluble matter was filtered off. The volatile components were removed from the filtrate by distillation under reduced pressure, yielding 30.0 g of crude product as a pale yellow solid. Recrystallization from 85% ethanol yielded 23.6 g (94% yield) of 2-(1-hydroxyethyl)-10H-phenothiazine (d-1) as a pale yellow solid. TIFF0007719880000037.tif25129

[0097] [Second step] (d-1)→(d-2): A 500 ml four-neck flask equipped with a magnetic stirrer and thermometer was charged with 21.4 g (87.9 mmol) of compound (d-1), 48.7 g (615 mmol) of pyridine, and 200 ml of dichloromethane. While maintaining the internal temperature below 15°C, 34.5 g (440 mmol) of acetyl chloride was added dropwise, and the reaction was continued for an additional hour. The reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. The extract was then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure, yielding 23.7 g (94% yield) of 2-(1-acetoxyethyl)-10H-phenothiazine (d-2). TIFF0007719880000038.tif25129

[0098] [3rd step] (d-2)→(d-3): A 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, gas inlet, and gas outlet was charged with 23.7 g (83.0 mmol) of compound (d-2) and 170 ml of N,N-dimethylformamide. While maintaining the internal temperature below 5°C, 3.0 g (125 mmol) of sodium hydride was added and the reaction was continued for 1 hour. 14.7 g (116 mmol) of benzyl chloride was then added and the reaction was continued for 1 hour at 60°C. The reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with ethyl acetate. The extract was then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure, yielding 34.9 g of crude 2-(1-acetoxyethyl)-10-benzyl-10H-phenothiazine (d-3). TIFF0007719880000039.tif30129

[0099] [4th step] (d-3)→(d-4): A 500 mL four-neck flask equipped with a magnetic stirrer, thermometer, and reflux condenser was charged with 34.9 g (approximately 83.0 mmol) of compound (d-3), 50 g of acetic acid, 56 g (494 mmol) of 30 wt% hydrogen peroxide, and 300 mL of toluene. The reaction was carried out at 50°C, 60°C, and 70°C for 1 hour each, and then at 80°C for 2 hours. The upper layer of the reaction mixture was removed and the volatile components were distilled off under reduced pressure to obtain 34.0 g of crude product. Recrystallization was carried out using a toluene / ethanol mixed solvent (1 / 1 by volume) to obtain 27.3 g of 2-(1-acetoxyethyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (d-4) (82% yield based on compound d-2). TIFF0007719880000040.tif33129 1 H NMR (400MHz, Acetone-d6) δppm (TMS) 1.31 (d, J=6.8Hz, 3H, C H 3CH(OCOCH3)-Ar) 1.85 (s, 3H, CH3CH(OCOC H 3)-Ar) 5.66 (s, 2H, Ar-C H 2) 5.78 (q, J=6.8Hz, 1H, CH3C H (OCOCH3)-Ar) 7.23-7.42 (m, 9H, Ar) 7.62 (t, J=8.4Hz, 1H, Ar) 8.04 (d, J=8.4Hz, 1H, Ar) 8.06 (dd, J=8.4Hz, 1H, Ar)

[0100] [5th step] (d-4)→(d-5): A 1000 ml four-neck flask equipped with a magnetic stirrer, thermometer, and reflux condenser was charged with 26.9 g (66.0 mmol) of compound (d-4), 18.5 g (330 mmol) of potassium hydroxide, 500 ml of methanol, and 150 ml of water, and the reaction was carried out at 70 °C for 2 hours. After the reaction was completed, the volatile components were distilled off under reduced pressure, and water was added to the residue. The product was extracted with dichloromethane. The mixture was then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were distilled off from the filtrate under reduced pressure, yielding 23.4 g of crude product. The mixture was recrystallized using methanol to obtain 22.2 g (92% yield) of 2-(1-hydroxyethyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (d-5) as a pale yellow solid. TIFF0007719880000041.tif33129 1 H NMR (400MHz, Acetone-d6) δppm (TMS) 1.31 (d, J=6.8Hz, 3H, C H 3CH(OH)-Ar) 2.82 (s, 1H, CH3CH(O H )-Ar ) 4.86 (quint, J=6.0Hz, 1H, CH3C H (O H )-Ar) 5.63 (s, 2H, Ar-C H 2) 7.24-7.45 (m, 9H, Ar) 7.57-7.63 (m, 1H, Ar) 8.01 (d, J=8.0Hz, 1H, Ar) 8.07 (dd, J=8.4Hz, 2.0Hz, 1H, Ar)

[0101] [6th step] (d-5)→(d-6): A 500 mL four-neck flask equipped with a magnetic stirrer, thermometer, gas inlet, and gas outlet was charged with 330 mL of dichloromethane and 14.4 g (113 mmol) of oxalyl chloride. After cooling the reaction vessel to -70 to -80 °C under a nitrogen atmosphere, 13.3 g (170 mmol) of dimethyl sulfoxide was slowly added dropwise and the temperature was maintained for 1 hour. 20.7 g (56.7 mmol) of compound (d-5), previously dissolved in 22 g of dimethyl sulfoxide, was added, and the reaction was continued at the same temperature for 2 hours. 34 g (337 mmol) of triethylamine was added, and the mixture was slowly warmed to room temperature. The reaction mixture was then poured into a saturated aqueous solution of sodium chloride. The product was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The insoluble material was then filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure, yielding 29.2 g of crude product. The crude product was subjected to column chromatography using dichloromethane as an eluent to obtain 17.8 g (yield 86%) of 2-acetyl-10-benzyl-10H-phenothiazine-5,5-dioxide (d-6) as a pale yellow solid. TIFF0007719880000042.tif33129 1 H NMR (400MHz, Chloroform-d) δppm (TMS) 2.50 (s, 3H, C H 3(C=O)-Ar) 5.48 (s, 2H, Ar-C H 2) 7.19 (d, J=8.8Hz, 3H, Ar) 7.28-7.40 (m, 4H, Ar) 7.52 (t,J=7.6Hz, 1H, Ar) 7.73 (s, 1H, Ar) 7.78 (d, J=8.4Hz, 1H, Ar) 8.15 (d, J=9.2Hz, 1H, Ar) 8.23 (d, J=8.4Hz, 1H, Ar)

[0102] [Step 7] (d-6)→(d): A 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, gas inlet, and gas outlet was charged with 200 ml of tetrahydrofuran and cooled to below 0°C under a nitrogen atmosphere. 8.2 g (73.5 mmol) of potassium tert-butoxide was added and the temperature was maintained for 10 minutes. Then, 26.3 g (73.5 mmol) of methyltriphenylphosphonium bromide was added and the temperature was maintained for 30 minutes. 17.8 g (49.0 mmol) of compound (d-6) was added and the reaction was carried out for 2 hours from below 0°C to room temperature. The reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. The mixture was then dried over anhydrous magnesium sulfate, after which insoluble matter was filtered off. Volatile components were removed from the filtrate under reduced pressure to obtain the crude product. The crude product was purified by column chromatography (carrier: Wakogel C-300) using dichloromethane as an eluent and recrystallized using ethyl acetate to obtain 8.4 g (yield 47%) of 2-(1-methylethenyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (d) as a colorless solid. TIFF0007719880000043.tif33129 1 H NMR (400MHz, Chloroform-d) δppm (TMS) 1.96 (s, 3H, CH2=C H (CH3)-Ar) 5.10 (s, 1H, CH2=C H (CH3)-Ar (trans to the Ar group) 5.22 (s, 1H, CH2=C H (CH3)-Ar (cis to the Ar group) 5.43(s, 2H, Ar-CH2-) 7.12-7.42 (m, 9H, Ar) 7.49 (t, J=8.8Hz, 1H, Ar) 8.08 (d, J=8.4Hz, 1H, Ar) 8.15 (d, J=7.6Hz, 1H, Ar)

[0103] Reference example 5 Compound (e) was produced from compound (b-2) obtained in the same manner as in Reference Example 2 by the following method. TIFF0007719880000044.tif24166 [3rd step] (b-2) → (e): 220 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, gas inlet tube, and gas outlet tube. The reaction vessel was cooled to below 10°C while purging with nitrogen. 8.4 g (74.9 mmol) of potassium tert-butoxide was added, followed by 26.9 g (75.3 mmol) of methyltriphenylphosphonium bromide, and the reaction was carried out for 30 minutes. 15.0 g (62.2 mmol) of compound (b-2) was added to the reaction mixture and the reaction was carried out for 2 hours at 10-30°C. The resulting reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. After drying over anhydrous magnesium sulfate, insoluble matter was filtered off, and the volatile components were removed from the filtrate under reduced pressure, yielding 35.1 g of residue. The residue was subjected to column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent to remove triphenylphosphine oxide, and then recrystallized from ethanol to obtain 8.1 g (yield 54%) of compound (e) as a pale yellow solid. TIFF0007719880000045.tif25129 1 H NMR (400MHz, CDCl3, δ ppm): 3.37 (s, 3H, NC H 3) 5.14 (d, J=10.8Hz, 1H, C H 2 = CH-Ar (trans to the Ar group) 5.61 (d, J=17.6Hz, 1H, C H 2 = CH-Ar (cis to Ar group) 6.59 (dd, J=10.8Hz, 17.6Hz, 1H, CH2=C H -Ar) 6.75 (d, J=8.4Hz, 1H, Ar) 6.81 (d, J=9.2Hz, 1H, Ar) 6.92 (td, J=7.6Hz, 1.2Hz, 1H, Ar) 7.11-7.23 (m, 4H, Ar)

[0104] Example 1 A separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a Dimroth condenser Within , Water 187 parts by weight Sodium lauryl sulfate 2 〃 Polyoxyethylene lauryl ether 2 Charged monomer mixture Ethyl acrylate (EA) 97.4 % Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (a) of Reference Example 1 1.0 After thoroughly removing oxygen from the system by replacing the chamber with oxygen, Sodium formaldehyde 0.008 parts by weight sulfoxylates (Fujifilm Wako Pure Chemicals product Rongalit) Tertiary butyl hydroperoxide 0.0047 〃 (NOF Products Perbutyl H-69) The polymerization reaction was initiated at room temperature by adding the above-mentioned solution, and the reaction was continued until the polymerization conversion rate reached 90% or more. The obtained aqueous latex was coagulated with a 10% by weight aqueous solution of sodium sulfate, then washed with water and dried to obtain acrylic rubber A. The Mooney viscosity PML of the obtained acrylic rubber A was 1+4 (100℃) was 32.

[0105] Its mole fraction composition is: 1 The δ ppm was calculated from H-NMR (400 MHz, Acetone-d6) using the following formula: Compound (a): 0.23 mol%, EA+MBF: 99.77 mol% It was. α: Integrated value of the signal between 7.0 and 8.2 ppm β: Integrated value of the signal between 3.2 and 5.0 ppm Compound (a) (mol%) = 200 × α / 9β EA + MBF (mol%) = 100 - Compound (a) The approximate weight fraction composition is calculated using the following formula: Compound (a): 0.87% by weight, EA+MBF: 99.13% by weight. Compound (a) (wt%) = (Compound (a) (mol%) × 380.3 × 100) / [Compound (a) (mol%) × 380.3 + (EA + MBF (mol%)) × 100.8)] EA+MBF(wt%)=100-Compound(a)(wt%)

[0106] Example 2 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain an acrylic rubber B. Mooney viscosity PML of the obtained acrylic rubber B 1+4 (100℃) was 27. Charged monomer mixture Ethyl acrylate [EA] 97.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (b) of Reference Example 2 1.0

[0107] Its mole fraction composition is: 1 The δ ppm was calculated from H-NMR (400 MHz, Acetone-d6) using the following formula: Compound (b): 0.36 mol%, EA+MBF: 99.64 mol% It was. α: Integrated value of the signal between 7.0 and 8.2 ppm β: Integrated value of the signal between 3.2 and 5.0 ppm Compound (b) (mol%) = 200 × α / (2α + 7β) EA + MBF (mol%) = 100 - Compound (b) The approximate weight fraction composition is calculated using the following formula: Compound (b): 1.03% by weight, EA+MBF: 98.97% by weight. Compound (b) (wt%) = (Compound (b) (mol%) × 271.34 × 100) / [Compound (b) (mol%) × 271.34 + (EA + MBF (mol%)) × 100.8)] EA+MBF(wt%)=100-compound(b)(wt%)

[0108] Example 3 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber C. Mooney viscosity PML of the obtained acrylic rubber C 1+4 (100℃) was 31. Charged monomer mixture Ethyl acrylate [EA] 97.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (c) of Reference Example 3 1.0

[0109] Its mole fraction composition is: 1 The formula was calculated from H-NMR (400 MHz, Acetone d6, δ ppm) using the following equation: Compound (c): 0.34 mol%, EA+MBF: 99.66 mol% It was. α: Integrated value of the signal between 7.0 and 8.2 ppm β: Integrated value of the signal between 3.2 and 5.0 ppm Compound (c) (mol%) = 200 × α / (2α + 7β) EA + MBF (mol%) = 100 - compound (c) The approximate weight fraction composition is calculated using the following formula: The compound (c): 1.01% by weight, and EA+MBF: 98.99% by weight. Compound (c) (wt%) = (Compound (c) (mol%) × 299.39 × 100) / [Compound (c) (mol%) × 299.39 + (EA + MBF (mol%)) × 100.8)] EA+MBF(wt%)=100-Compound(c)(wt%)

[0110] Example 4 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber D. Mooney viscosity PML of the obtained acrylic rubber D 1+4(100℃) was 33. Charged monomer mixture Ethyl acrylate [EA] 97.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (d) of Reference Example 4 1.0

[0111] Its mole fraction composition is: 1 The δ ppm was calculated from H-NMR (400 MHz, Acetone-d6) using the following formula: Compound (d): 0.27 mol%, EA+MBF: 99.73 mol% It was. α: Integrated value of the signal between 7.0 and 8.2 ppm β: Integrated value of the signal between 3.2 and 5.0 ppm Compound (d) (mol%) = 200 × α / (α + 6β) EA + MBF (mol%) = 100 - Compound (d) The approximate weight fraction composition is calculated using the following formula: Compound (d): 0.96% by weight, EA+MBF: 99.04% by weight. Compound (d) (wt%) = (Compound (d) (mol%) × 361.34 × 100) / [Compound (d) (mol%) × 361.34 + (EA + MBF (mol%)) × 100.8)] EA+MBF(wt%)=100-compound(d)(wt%)

[0112] Reference Comparative Example 1 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber E. Mooney viscosity PML of the obtained acrylic rubber E 1+4 (100℃) was 32. Charged monomer mixture Ethyl acrylate [EA] 98.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃

[0113] Example 5 Acrylic rubber A 100 parts by weight FEF Carbon Black 60% (Tokai Carbon Products Seast GS0) Stearic acid (Miyoshi Oil Products TST) 1 〃 Polyoxyethylene stearyl ether phosphate 0.5% (Toho Chemical Industry Products Phosphanol RL-210) Crosslinking accelerator (Vulcofac ACT55, Safic-Alcan) 1 Hexamethylenediamine carbamate 0.6 〃 (Unimatec Cheminox AC6F) Of the above components, acrylic rubber A, FEF carbon black, stearic acid, and polyoxyethylene stearyl ether phosphate were mixed in a Banbury mixer. The remaining components were mixed with the resulting mixture in an open roll to obtain an acrylic rubber composition.

[0114] This was subjected to primary crosslinking at 180°C for 8 minutes and oven crosslinking (secondary crosslinking) at 175°C for 4 hours using a 100-ton press molding machine, resulting in a sheet-like crosslinked product with a thickness of approximately 2 mm and a cylindrical crosslinked product with a diameter of approximately 29 mm and a height of approximately 12.5 mm. The crosslinking characteristics of the acrylic rubber composition and the physical properties of the crosslinked product were measured as follows. Mooney scorch test: JIS K6300-1 compliant (125°C) Toyo Seiki Mooney Viscometer AM-3 Using the minimum Mooney viscosity (ML, min) and the Measure the value of the time (t5) Crosslinking test: JIS K6300-2 compliant (180°C, 12 minutes) Using a rotorless rheometer RLR-3 manufactured by Toyo Seiki Seisakusho, Measure the values of ML, MH, tc(10) and tc(90) ML: Minimum torque MH: Maximum torque tc(10): The time it takes for the cross-linking torque to reach ML + (MH-ML) × 0.1 Time required tc(90): The time it takes for the cross-linking torque to reach ML + (MH-ML) × 0.9 Time required Normal state physical properties: Compliant with JIS K6251 and JIS K6253 Air heating aging test: JIS K6257 compliant (190℃: 100 hours, 200 hours, 300 hours, 400 hours, 500 hours) (175℃: 70 hours, 250 hours, 500 hours, 750 hours, 1000 hours) Oil immersion test: In accordance with JIS K6258, 150°C, 168 hours in oil (IRM903 After immersion in oil, Example 6 and Comparative Examples 1 and 2 The hardness change compared to the normal physical properties before immersion in oil, The other change rates and volume swelling ratios were calculated. Oil immersion-air heat aging combined test: In accordance with JIS K6258, 150°C, 168 hours of oil (IRM903 After immersion in oil, wipe off the oil from the test piece and In accordance with the standard, an air heating aging test was conducted at 190°C for 200 hours. Compared with the normal physical properties before immersion in oil Compression set test: JIS K6262 compliant (175°C: 70 hours)

[0115] Example 6 In Example 5, acrylic rubber B was used instead of acrylic rubber A.

[0116] Example 7 In Example 5, acrylic rubber C was used in place of acrylic rubber A.

[0117] Example 8 In Example 5, acrylic rubber D was used in place of acrylic rubber A.

[0118] Comparative Example 1 In Example 5, acrylic rubber E was used in place of acrylic rubber A.

[0119] Comparative Example 2 In Comparative Example 1, 1.0 part by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD, a product of Ouchi Shinko Chemical Industry Co., Ltd.) was further added.

[0120] The results obtained in Examples 5 to 8 and Comparative Examples 1 and 2 are shown in Table 1 below. Table 1 Measurement results Fruit-5 Fruit-6 Fruit-7 Fruit-8 ratio-1 ratio-2 Mooney scorch test (125℃) ML min (pts) 71 71 69 70 72 70 t5 (min) 3.8 3.7 4.0 3.8 3.1 3.3 Cross-linking test (180℃) tc(10) (min) 0.52 0.55 0.56 0.53 0.51 0.51 tc(90) (min) 5.62 5.67 5.50 5.55 5.26 5.19 ML (N m) 0.29 0.30 0.30 0.30 0.29 0.30 MH (N m) 0.96 1.00 0.99 1.04 1.08 1.08 Normal physical properties Hardness (Duro A) 68 71 71 72 71 69 100% Modulus (MPa) 5.1 6.0 5.9 6.3 6.1 5.7 Strength at break (MPa) 17.0 17.2 17.2 17.2 17.6 16.8 Elongation at break (%) 260 240 250 230 230 230 Heat aging test (190℃, 100 hours) Hardness Change (Duro A) +10 +7 +7 +5 +6 +4 100% Modulus Change (%) -21 -32 -39 -40 -48 -40 Strength change rate at break (%) -31 -46 -49 -49 -56 -42 Change in elongation at break (%) +14 +14 +26 +26 +26 +39 Heat aging test (190℃, 200 hours) Hardness Change (Duro A) +9 +8 +7 +5 +8 +4 100% Modulus Change (%) -34 -37 -42 -44 -39 -51 Strength change rate at break (%) -54 -61 -65 -65 -66 -64 Change in elongation at break (%) +13 +5 +13 +19 -39 +32 Heat aging test (190℃, 300 hours) Hardness Change (Duro A) +19 +19 +16 +17 +20 +15 100% Modulus Change (%) -8 -3 -10 -11 -18 Strength change rate at break (%) -67 -63 -67 -65 -58 -68 Elongation change at break (%) -26 -37 -39 -43 -78 -21 Heat aging test (190℃, 400 hours) Hardness Change (Duro A) +20 +19 +20 +19 +22 +19 100% Modulus Change (%) Strength change rate at break (%) -61 -54 -59 -61 -46 -61 Elongation change at break (%) -66 -65 -69 -78 -93 -71 Heat aging test (190℃, 500 hours) Hardness Change (Duro A) +29 +26 +25 +23 +28 +24 100% Modulus Change (%) Strength change rate at break (%) -36 -21 -24 -24 -26 -28 Change in elongation at break (%) -90 -91 -92 -94 -99 -93 Heat aging test (175℃, 70 hours) Hardness Change (Duro A) +5 +6 +3 +2 +5 +3 100% Modulus Change (%) -6 -2 -17 -16 -18 -32 Strength change rate at break (%) -9 -12 -16 -12 -17 -18 Change in elongation at break (%) +5 +4 +8 +13 +7 +17 Heat aging test (175℃, 250 hours) Hardness Change (Duro A) +9 +9 +7 +6 +1 +3 100% Modulus Change (%) -10 -23 -32 -37 -39 -35 Strength change rate at break (%) -28 -38 -41 -48 -48 -37 Change in elongation at break (%) +12 +19 +19 +32 +28 +32 Heat aging test (175℃, 500 hours) Hardness Change (Duro A) +16 +13 +13 +12 +13 +9 100% Modulus Change (%) -18 -23 -31 -35 -20 -44 Strength change rate at break (%) -54 -59 -64 -63 -65 -65 Change in elongation at break (%) +10 +7 +11 +18 -9 +40 Heat aging test (175℃, 750 hours) Hardness Change (Duro A) +18 +17 -16 +18 +22 +16 100% Modulus Change (%) -6 +0 -7 -10 -19 Strength change rate at break (%) -62 -60 -63 -62 -51 -65 Change in elongation at break (%) -4 -20 -15 -12 -59 +8 Heat aging test (175℃, 1000 hours) Hardness Change (Duro A) +25 +25 +23 +25 +27 +25 100% Modulus Change (%) Strength change rate at break (%) -53 -30 -35 -33 +31 -46 Change in elongation at break (%) -70 -73 -73 -75 -96 -77 Oil immersion test (150°C, 168 hours) Hardness change (Duro A) - -10 - - -8 -6 100% Modulus Change Rate (%) - -8 - - -2 +3 Strength change rate at break (%) - -4 - - -5 -3 Elongation change rate at break (%) - -4 - - -1 -7 Volume swelling rate (%) - +11 - - +11 +10 Oil immersion-air heating aging combined test Hardness Change (Duro A) +15 +15 +12 +15 +17 +17 100% Modulus Change (%) -2 -17 -20 -24 +3 +9 Strength change rate at break (%) -51 -59 -61 -62 -59 -58 Change in elongation at break (%) -8 -12 -7 -6 -42 -41 Compression set test (175℃, 70 hours) (%) 19 17 17 17 16 15

[0121] Example 9 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber F. Mooney viscosity PML of the obtained acrylic rubber F 1+4 (100℃) was 31. Charged monomer mixture Ethyl acrylate [EA] 97.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (e) of Reference Example 5 1.0

[0122] Its mole fraction composition is: 1 The δ ppm was calculated from H-NMR (400 MHz, Acetone-d6) using the following formula: Compound (e): 0.41 mol%, EA+MBF: 99.59 mol% It was. α: integral value of the signal between 6.5 and 7.5 ppm β: Integrated value of the signal between 3.2 and 5.0 ppm Compound (e) (mol%) = 200 × α / (2α + 7β) EA + MBF (mol%) = 100 - Compound (e) The approximate weight fraction composition is calculated using the following formula: The compound (e): 1.0% by weight, and EA+MBF: 99.0% by weight. Compound (e) (wt%) = (Compound (e) (mol%) × 239.34 × 100) / [Compound (e) (mol%) × 239.34 + (EA + MBF (mol%)) × 100.8)] EA+MBF(wt%)=100-compound(e)(wt%)

[0123] Example 10 In Example 5, SRF carbon black (Tokai Carbon Products, SEAST GS) was used in place of FEF carbon black (SEAST GS0), and acrylic rubber F was used in place of acrylic rubber A.

[0124] Comparative Example 3 In Example 10, acrylic rubber E was used in place of acrylic rubber F.

[0125] Comparative Example 4 In Comparative Example 3, 1.0 part by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was further added.

[0126] The results obtained in Example 10 and Comparative Examples 3 and 4 are shown in Table 2 below. Example 10 and Comparative Examples 3 and 4 were further subjected to a combined air heating aging-oil immersion-air heating aging test under the following test conditions. Combined air aging-oil immersion-air aging test: Air heating at 175°C for 150 hours in accordance with JIS K6257 Aging tests were conducted in accordance with JIS K6258 at 150°C for 168 hours. An oil (IRM903 oil) immersion test was performed, and the oil on the test piece was wiped off. and then tested under conditions of 190°C for 300 hours in accordance with JIS K6257. The air heating aging test was carried out and the physical properties were compared with those of the normal state before the test. Ta Table 2 Measurement results Fruit-10 ratio-3 ratio-4 Mooney scorch test (125℃) ML min (pts) 65 65 64 t5 (min) 1.5 2.8 2.4 Cross-linking test (180℃) tc(10) (min) 0.52 0.51 0.50 tc(90) (min) 5.43 4.93 4.87 ML (N·m) 0.24 0.22 0.23 MH (N m) 0.96 0.98 0.97 Normal physical properties Hardness (Duro A) 65 64 63 100% Modulus (MPa) 5.2 4.2 4.4 Strength at break (MPa) 17.1 17.1 15.8 Elongation at break (%) 260 270 260 Heat aging test (190℃, 100 hours) Hardness Change (Duro A) +9 +3 +0 100% Modulus Change (%) +62 -48 -36 Strength change rate at break (%) -8 -65 -35 Change in elongation at break (%) -30 +19 +28 Heat aging test (190℃, 200 hours) Hardness Change (Duro A) +10 +12 +0 100% Modulus Change (%) +37 -24 -52 Strength change rate at break (%) -23 -68 -60 Change in elongation at break (%) -30 -30 +31 Heat aging test (190℃, 300 hours) Hardness Change (Duro A) +13 +20 +3 100% Modulus Change (%) +17 +26 -48 Strength change rate at break (%) -41 -68 -70 Change in elongation at break (%) -29 -61 +33 Heat aging test (190℃, 400 hours) Hardness Change (Duro A) +16 +28 +15 100% Modulus Change (%) +8 -25 Strength change rate at break (%) -57 -56 -69 Elongation change at break (%) -42 -86 -11 Heat aging test (190℃, 500 hours) Hardness Change (Duro A) +24 +31 +23 100% Modulus Change (%) +31 +14 Strength change rate at break (%) -58 -31 -65 Elongation change at break (%) -61 -93 -51 Oil immersion test (150°C, 168 hours) Hardness change (Duro A) -6 -7 -7 100% Modulus Change (%) -6 +12 +5 Strength change rate at break (%) -10 -9 -6 Elongation change at break (%) -4 -9 -6 Volume swelling rate (%) +11 +11 +10 Oil immersion-air heating aging combined test Hardness Change (Duro A) +13 +13 +12 100% Modulus Change (%) +38 -12 -20 Strength change rate at break (%) -30 -65 -61 Elongation change at break (%) -37 -31 -18 Air heating aging-oil immersion-air heating aging combined test Hardness Change (Duro A) +17 +23 +19 100% Modulus Change Rate (%) +15 +9 Strength change rate at break (%) -51 -61 -68 Elongation change at break (%) -39 -71 -60 Compression set test (175℃, 70 hours) (%) 14 14 14

[0127] Example 11 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber G. Mooney viscosity PML of the obtained acrylic rubber G 1+4 (100℃) was 30. Charged monomer mixture Ethyl acrylate [EA] 97.9 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (e) of Reference Example 5 0.5

[0128] Its mole fraction composition is: The compound (e): 0.20 mol %, EA+MBF: 99.80 mol %. The approximate weight fraction composition was compound (e): 0.48 wt %, EA+MBF: 99.52 wt %.

[0129] Example 12 In Example 5, the following ingredients were used: Acrylic rubber G 100 parts by weight SRF Carbon Black (Seast GS) 70 Stearic acid (TST) 1 〃 Polyoxyethylene stearyl ether phosphate 0.5% (Phosphanol RL-210) Stearylamine 1 〃 (Kao product Farmin 80S) Crosslinking accelerator (Vulcofac ACT55) 1 〃 Hexamethylenediamine carbamate 0.6 〃 (ChemiNox AC6F)

[0130] Comparative Example 5 In Example 12, Acrylic Rubber E was used instead of Acrylic Rubber G.

[0131] Comparative Example 6 In Comparative Example 5, 0.5 parts by weight of the compound (b-1) prepared in Reference Example 5 was further used.

[0132] Comparative Example 7 In Comparative Example 5, 0.5 parts by weight of compound (e) was further used.

[0133] The results obtained in Example 12 and Comparative Examples 5 to 7 are shown in Table 3 below. Table 3 Measurement results Fruit-12 ratio-5 ratio-6 ratio-7 Mooney scorch test (125℃) ML min (pts) 59 61 58 58 t5 (min) 4.2 3.8 4.0 4.0 Cross-linking test (180℃) tc(10) (min) 0.58 0.57 0.57 0.56 tc(90) (min) 6.62 6.58 6.54 6.54 ML (N m) 0.26 0.26 0.26 0.26 MH (N m) 0.95 1.00 0.99 0.95 Normal physical properties Hardness (Duro A) 70 70 69 70 100% Modulus (MPa) 5.1 5.6 6.0 5.5 Strength at break (MPa) 15.5 15.3 15.4 14.6 Elongation at break (%) 270 240 240 260 Heat aging test (190℃, 100 hours) Hardness Change (Duro A) +10 +7 +6 +9 100% Modulus Change (%) +27 -38 -42 -24 Strength change rate at break (%) -9 -47 -49 -29 Elongation change at break (%) -20 +7 +6 -1 Heat aging test (190℃, 200 hours) Hardness Change (Duro A) +9 +9 +11 +10 100% Modulus Change (%) +10 -29 -37 -38 Strength change rate at break (%) -25 -59 -59 -58 Elongation change at break (%) -14 -10 -9 -3 Heat aging test (190℃, 300 hours) Hardness Change (Duro A) +15 +20 +23 +21 100% Modulus Change (%) -2 +7 Strength change rate at break (%) -49 -56 -55 -57 Elongation change at break (%) -22 -66 -62 -55 Heat aging test (190℃, 400 hours) Hardness Change (Duro A) +17 +25 +24 +23 100% Modulus Change Rate (%) +10 Strength change rate at break (%) -54 -29 -32 -37 Elongation change at break (%) -37 -86 -86 -82 Heat aging test (190℃, 500 hours) Hardness Change (Duro A) +21 +25 +28 +24 100% Modulus Change (%) +41 Strength change rate at break (%) -52 +11 +5 +0 Elongation change at break (%) -60 -96 -96 -95 Heat aging test (190℃, 600 hours) Hardness Change (Duro A) +24 +29 +28 +27 100% Modulus Change (%) Strength change rate at break (%) -11 -7 -16 -32 Elongation change at break (%) -92 -100 -100 -100 Compression set test (175℃, 70 hours) (%) 21 20 20 21 (175℃, 500 hours) (%) 38 36 36 35

[0134] Example 13 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber H. Mooney viscosity PML of the obtained acrylic rubber H 1+4 (100℃) was 38. Charged monomer mixture Ethyl acrylate [EA] 97.0 parts by weight Vinyl chloroacetate (VCA) 2.5 % Compound (e) of Reference Example 5 0.5

[0135] Its approximate mole fraction composition is The compound (e): 0.22 mol %, EA+VCA: 99.78 mol %. The approximate weight fraction composition was: Compound (e): 0.51 wt %; EA+VCA: 99.49 wt %.

[0136] Reference Comparative Example 2 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber J. Mooney viscosity PML of the obtained acrylic rubber J 1+4 (100℃) was 43. Charged monomer mixture Ethyl acrylate [EA] 97.5 parts by weight Vinyl chloroacetate (VCA) 2.5 %

[0137] Example 14 In Example 5, the following ingredients were used: Acrylic rubber H 100 parts by weight FEF Carbon Black (Seast GSO) 60 Stearic acid (TST) 1 〃 Sodium fatty acid (Kao Chemical product Na-soap) 3 Same Fatty acid potassium (NOF Products Nonsal SK-1) 0.25 Sulfur (Hosoi Chemical Products Precipitated Sulfur) 0.3 〃

[0138] Comparative Example 8 In Example 14, Acrylic Rubber J was used instead of Acrylic Rubber H.

[0139] Comparative Example 9 In Comparative Example 8, 1.0 part by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was further added.

[0140] Example 15 In Example 5, the following ingredients were used: Acrylic rubber H 100 parts by weight FEF Carbon Black (Seast GSO) 60 Stearic acid (TST) 1 〃 2,4,6-trimercapto-s-triazine 0.5 〃 (Ouchi Shinko Chemical Products Noccela TCA) Zinc dibutyldithiocarbamate 1.5 〃 (Ouchi Shinko Chemical Products Noccela BZ)

[0141] Comparative Example 10 In Example 15, Acrylic Rubber J was used instead of Acrylic Rubber H.

[0142] Comparative Example 11 In Comparative Example 10, 1.0 part by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was further added.

[0143] The results obtained in Examples 14 to 15 and Comparative Examples 8 to 11 are shown in Table 4 below. Table 4 Measurement results Fruit-14 ratio-8 ratio-9 Fruit-15 ratio -10 ratio-11 Mooney scorch test (125℃) ML min (pts) 67 71 69 60 59 60 t5 (min) 7.6 8.0 7.3 11.1 7.3 9.4 Cross-linking test (180℃) tc(10) (min) 0.88 0.92 0.93 1.54 1.46 1.46 tc(90) (min) 4.82 4.44 4.43 6.64 6.30 6.22 ML (N m) 0.29 0.30 0.30 0.27 0.28 0.26 MH (N m) 1.14 1.21 1.19 1.18 1.30 1.24 Normal physical properties Hardness (Duro A) 67 67 66 68 69 69 100% Modulus (MPa) 5.8 6.2 6.4 6.3 7.0 7.0 Strength at break (MPa) 16.5 15.9 15.6 14.7 14.8 14.6 Elongation at break (%) 280 280 280 280 260 240 Heat aging test (150℃, 70 hours) Hardness Change (Duro A) +4 +6 +6 +7 +6 +6 100% Modulus Change (%) +14 -13 -17 +14 +1 -11 Strength change rate at break (%) +7 -3 -6 +14 +1 -3 Change in elongation at break (%) -10 -7 +0 -18 -9 +12 Heat aging test (150℃, 200 hours) Hardness Change (Duro A) +4 +4 +5 +6 +6 +5 100% Modulus Change (%) +14 -31 -30 +19 +4 -14 Strength change rate at break (%) +8 -15 -7 +17 +10 +0 Change in elongation at break (%) -10 +1 +13 -21 -7 +12 Heat aging test (150℃, 400 hours) Hardness Change (Duro A) +19 +19 +16 +17 +20 +15 100% Modulus Change (%) -8 -3 -10 -11 -18 Strength change rate at break (%) -67 -63 -67 -65 -58 -68 Elongation change at break (%) -26 -37 -39 -43 -78 -21 Heat aging test (150℃, 600 hours) Hardness Change (Duro A) +20 +19 +20 +19 +22 +19 100% Modulus Change (%) Strength change rate at break (%) -61 -54 -59 -61 -46 -61 Elongation change at break (%) -66 -65 -69 -78 -93 -71 heat Aging test (150℃, 800 hours) Hardness Change (Duro A) +29 +26 +25 +23 +28 +24 100% Modulus Change (%) Strength change rate at break (%) -36 -21 -24 -24 -26 -28 Change in elongation at break (%) -90 -91 -92 -94 -99 -93 Heat aging test (150℃, 1000 hours) Hardness Change (Duro A) +5 +6 +3 +2 +5 +3 100% Modulus Change (%) -6 -2 -17 -16 -18 -32 Strength change rate at break (%) -9 -12 -16 -12 -17 -18 Change in elongation at break (%) +5 +4 +8 +13 +7 +17 Heat aging test (175℃, 100 hours) Hardness Change (Duro A) +5 +2 +6 +9 +6 +7 100% Modulus Change (%) -17 -65 -50 +3 -37 -27 Strength change rate at break (%) -14 -78 -34 +9 -26 -10 Change in elongation at break (%) +0 +30 +30 -13 -5 +16 Heat aging test (175℃, 200 hours) Hardness Change (Duro A) +6 +11 +5 +9 +10 +9 100% Modulus Change (%) -36 -60 -67 -11 -60 -43 Strength change rate at break (%) -40 -79 -70 -10 -68 -29 Change in elongation at break (%) +17 +0 +78 -9 +18 +26 Heat aging test (175℃, 300 hours) Hardness Change (Duro A) +8 +18 +8 +14 +16 +9 100% Modulus Change (%) -48 -29 -75 -29 -61 -60 Strength change rate at break (%) -58 -72 -84 -33 -82 -58 Change in elongation at break (%) +25 -63 +86 -5 -6 +41 Heat aging test (175℃, 400 hours) Hardness Change (Duro A) +10 +23 +6 +13 +20 +8 100% Modulus Change (%) -57 -73 -41 -69 Strength change rate at break (%) -68 -66 -88 -48 -76 -77 Change in elongation at break (%) +28 -82 +70 +0 -64 +78 Heat aging test (175℃, 500 hours) Hardness Change (Duro A) +12 +28 +13 +16 +25 +14 100% Modulus Change (%) -55 -67 -49 -71 Strength change rate at break (%) -75 -45 -85 -66 +59 -86 Change in elongation at break (%) +18 -94 +44 +6 -84 +89 Compression set test (150℃, 70 hours) (%) 25 24 24 14 14 15 (175℃, 70 hours) (%) 41 43 40 26 28 25

[0144] Example 16 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber K. Mooney viscosity PML of the obtained acrylic rubber K 1+4 (100℃) was 36. Charged monomer mixture Ethyl acrylate [EA] 97.25 parts by weight Vinyl chloroacetate (VCA) 2.5 % Compound (e) of Reference Example 5 0.25 〃

[0145] Its approximate mole fraction composition is Compound (e): 0.096 mol %, EA+VCA: 99.904 mol %. The approximate weight fraction composition was: Compound (e): 0.23 wt %; EA+VCA: 99.77 wt %.

[0146] Example 17 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber L. Mooney viscosity PML of the obtained acrylic rubber L 1+4 (100℃) was 38. Charged monomer mixture Ethyl acrylate [EA] 97.4 parts by weight Vinyl chloroacetate (VCA) 2.5 % Compound (e) of Reference Example 5 0.1 〃

[0147] Its approximate mole fraction composition is Compound (e): 0.047 mol %, EA+VCA: 99.953 mol %. The approximate weight fraction composition was: Compound (e): 0.11 wt %; EA+VCA: 99.89 wt %.

[0148] Example 18 In Example 14, acrylic rubber K was used instead of acrylic rubber H. A combined oil immersion / air heating aging test was also conducted. Oil immersion-air heat aging combined test: In accordance with JIS K6258, 150℃, 168 hours of oil (IRM903 oil) After immersion in water, the specimen was subjected to 175°C for 300 hours in accordance with JIS K6257. The air heating aging test was carried out at , and the normal physical state before immersion in oil was We compared.

[0149] Example 19 In Example 14, Acrylic Rubber L was used instead of Acrylic Rubber H.

[0150] Comparative Example 12 In Comparative Example 8, 2.0 parts by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was further added.

[0151] The results obtained in Examples 18 to 19 and Comparative Example 12 are shown in Table 5 below. Table 5 Measurement results Fruit-18 Fruit-19 ratio-12 Mooney scorch test (125℃) ML min (pts) 66 65 64 t5 (min) 6.3 6.2 6.4 Cross-linking test (180℃) tc(10) (min) 0.86 0.86 0.82 tc(90) (min) 4.83 4.74 4.94 ML (N·m) 0.31 0.32 0.27 MH (N·m) 1.16 1.21 1.09 Normal physical properties Hardness (Duro A) 67 69 65 100% Modulus (MPa) 6.2 6.2 5.6 Strength at break (MPa) 15.8 15.2 14.8 Elongation at break (%) 290 270 300 Heat aging test (175℃, 100 hours) Hardness Change (Duro A) +9 +6 +8 100% Modulus Change (%) -34 -42 -46 Strength change rate at break (%) -29 -39 -38 Change in elongation at break (%) +8 +22 +38 Heat aging test (175℃, 200 hours) Hardness Change (Duro A) +7 +8 +7 100% Modulus Change (%) -55 -66 -63 Strength change rate at break (%) -52 -74 -61 Change in elongation at break (%) +22 +50 +62 Heat aging test (175℃, 300 hours) Hardness Change (Duro A) +11 +8 +9 100% Modulus Change (%) -61 -68 -68 Strength change rate at break (%) -73 -84 -78 Change in elongation at break (%) +31 +54 +88 Heat aging test (175℃, 400 hours) Hardness Change (Duro A) +13 +14 +11 100% Modulus Change (%) -61 -60 -71 Strength change rate at break (%) -81 -80 -83 Change in elongation at break (%) +26 +13 +83 Heat aging test (175℃, 500 hours) Hardness Change (Duro A) +13 +16 +9 100% Modulus Change (%) -55 -44 -73 Strength change rate at break (%) -77 -76 -87 Change in elongation at break (%) +2 -30 +72 Oil immersion-air heating aging combined test Hardness Change (Duro A) +12 +11 +17 100% Modulus Change (%) -55 -63 -52 Strength change rate at break (%) -71 -82 -78 Change in elongation at break (%) +20 +41 -12 Compression set test (150℃, 70 hours) (%) 24 24 25

[0152] Example 20 A copolymerization reaction was carried out in the same manner as in Example 11 except that the following charged monomer mixture was used to obtain an acrylic rubber M. Mooney viscosity PML of the obtained acrylic rubber M 1+4 (100℃) was 32. Charged monomer mixture Ethyl acrylate [EA] 98.2 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (e) of Reference Example 5 0.2 〃

[0153] Its mole fraction composition is: The compound (e): 0.085 mol %, EA+MBF: 99.915 mol %. The approximate weight fraction composition was compound (e): 0.20 wt %, EA+MBF: 99.80 wt %.

[0154] Example 21 A copolymerization reaction was carried out in the same manner as in Example 11 except that the following charged monomer mixture was used to obtain Acrylic Rubber N. Mooney viscosity PML of the obtained Acrylic Rubber N 1+4 (100℃) was 32. Charged monomer mixture Ethyl acrylate [EA] 98.3 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (e) of Reference Example 5 0.1 〃

[0155] Its mole fraction composition is: Compound (e): 0.047 mol %, EA+MBF: 99.953 mol %. The approximate weight fraction composition was compound (e): 0.11 wt %, EA+MBF: 99.89 wt %.

[0156] Example 22 Acrylic rubber G obtained in Examples 11, 20, 21 and Reference Comparative Example 1 , M, N and E were subjected to a heating test in air at 150°C for 3 hours, and the Mooney viscosity (PML) before and after the test was measured. 1+4 (100°C) were compared. The results obtained are shown in Table 6 below. Table 6 acrylic rubber E G M N Approximate copolymerization amount of compound (e) (wt%) 0 0.48 0.20 0.11 PML before heating test 1+4 (100℃) 32 30 32 32 PML after heating test1+4 (100℃) 9 30 31 33

[0157] Example 23 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following monomer mixture was used, to obtain an acrylic rubber P. Mooney viscosity PML of the obtained acrylic rubber P 1+4 (100℃) was 36. Charged monomer mixture Ethyl acrylate [EA] 97.3 parts by weight Vinyl chloroacetate (VCA) 2.5 % Compound (e) of Reference Example 5 0.2 〃

[0158] Its approximate mole fraction composition is The compound (e): 0.080 mol %, EA+VCA: 99.920 mol %. The approximate weight fraction composition was: Compound (e): 0.19 wt %; EA+VCA: 99.81 wt %.

[0159] Example 24 Acrylic rubber H obtained in Examples 13, 23, 17 and Reference Comparative Example 2 The same test as in Example 22 was carried out except that , P, L and J were used. The results obtained are shown in Table 7 below. Table 7 acrylic rubber J H P L Approximate copolymerization amount of compound (e) (wt%) 0 0.51 0.19 0.11 PML before heating test 1+4 (100℃) 43 38 36 38 PML after heating test 1+4 (100℃) 8 34 34 33

[0160] Example 25 In Example 5, the following ingredients were used: Acrylic rubber G 100 parts by weight FEF Carbon Black (Seast GSO) 60 Stearic acid (TST) 1 〃 Polyoxyethylene stearyl ether phosphate 0.5% (Phosphanol RL-210) Stearylamine 1 〃 (Kao product Farmin 80S) Crosslinking accelerator (Vulcofac ACT55) 1 〃 Hexamethylenediamine carbamate 0.6 〃 (ChemiNox AC6F) Additionally, a combined oil immersion and air heating aging test was conducted. Oil immersion-air heat aging combined test: In accordance with JIS K6258, 150°C, 168 hours in oil (IRM903 oil) After immersion in the PET bottle, the specimen was subjected to JIS K6257 conditions of 190°C for 200 hours. Air heating aging test was carried out under the following conditions, and the normal condition before oil immersion was confirmed. compared with sex.

[0161] Example 26 In Example 25, Acrylic Rubber M was used in place of Acrylic Rubber G.

[0162] Example 27 In Example 25, Acrylic Rubber N was used instead of Acrylic Rubber G.

[0163] Comparative Example 13 In Example 25, acrylic rubber E was used in place of acrylic rubber G, and 2.0 parts by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was further added.

[0164] Comparative Example 14 In Comparative Example 13, the amount of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) added was changed from 2.0 parts by weight to 1.0 part by weight.

[0165] Comparative Example 15 In Comparative Example 13, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was not used.

[0166] The results obtained in Examples 25 to 27 and Comparative Examples 13 to 15 are shown in Table 8 below. Table 8 Measurement results Fruit -25 Fruit-26 Fruit-27 ratio-13 ratio-14 ratio -15 Mooney scorch test (125℃) ML min (pts) 65 62 62 61 62 64 t5 (min) 4.2 3.9 4.2 4.2 4.2 3.8 Cross-linking test (180℃) tc(10) (min) 0.62 0.59 0.59 0.61 0.62 0.51 tc(90) (min) 6.68 6.62 6.54 6.53 6.56 6.40 ML (N m) 0.31 0.30 0.31 0.27 0.28 0.27 MH (N m) 0.94 0.98 1.00 0.93 0.96 0.99 Normal physical properties Hardness (Duro A) 70 70 69 67 70 69 100% Modulus (MPa) 5.8 5.6 5.6 4.8 4.9 4.9 Strength at break (MPa) 16.1 15.9 16.0 15.1 15.0 16.0 Elongation at break (%) 280 270 260 280 270 260 Heat aging test (175℃, 200 hours) Hardness Change (Duro A) +13 +10 +8 +12 +6 +8 100% Modulus Change (%) +31 +8 -2 -21 -8 -18 Strength change rate at break (%) -7 -9 -18 -28 -20 -32 Change in elongation at break (%) -24 -10 +0 +18 +10 +7 Heat aging test (175℃, 400 hours) Hardness Change (Duro A) +13 +12 +12 +10 +8 +10 100% Modulus Change (%) +17 -11 -23 -29 -27 -29 Strength change rate at break (%) -24 -31 -44 -41 -37 -58 Elongation change at break (%) -26 -8 -2 +17 +16 +0 Heat aging test (175℃, 600 hours) Hardness Change (Duro A) +12 +12 +15 +12 +11 +17 100% Modulus Change (%) -5 -25 -23 -35 -33 -2 Strength change rate at break (%) -45 -57 -63 -59 -58 -63 Change in elongation at break (%) -22 -7 -14 +25 +15 -36 Heat aging test (175℃, 800 hours) Hardness Change (Duro A) +17 +17 +20 +16 +14 +25 100% Modulus Change (%) -9 -9 +2 -38 -22 Strength change rate at break (%) -58 -62 -61 -69 -65 -58 Change in elongation at break (%) -35 -37 -51 +12 -7 -68 Heat aging test (190℃, 100 hours) Hardness Change (Duro A) +11 +10 +10 +9 +7 +10 100% Modulus Change (%) +16 -7 -11 -25 -24 -27 Strength change rate at break (%) -14 -21 -29 -33 -29 -49 Change in elongation at break (%) -19 -8 -4 +15 +12 +5 Heat aging test (190℃, 200 hours) Hardness Change (Duro A) +13 +13 +15 +14 +11 +15 100% Modulus Change (%) -5 -25 -25 -35 -29 -4 Strength change rate at break (%) -42 -54 -63 -61 -59 -66 Change in elongation at break (%) -23 -14 -27 +17 +2 -48 Oil immersion-air heating aging combined test Hardness Change (Duro A) +15 +13 +16 +18 +14 +15 100% Modulus Change (%) +10 -13 -20 -13 -10 -14 Strength change rate at break (%) -32 -41 -51 -58 -55 -59 Elongation change at break (%) -25 -10 -11 -23 -22 -24 Compression set test (175℃, 70 hours) (%) 23 21 21 20 22 22 (175℃, 500 hours) (%) 41 38 38 36 37 38

[0167] From the above results, the following can be said: (1) The data of the air heating aging test of Examples 5 to 8 show that the cross-linked acrylic rubber copolymerized with the copolymerizable antioxidant is stabilized against thermal oxidative degradation. In contrast, in Comparative Example 1 in which no copolymerizable antioxidant was copolymerized, the rate of change in elongation at break dropped sharply after 100 hours in the 190°C air heating aging test (FIGS. 1 to 4). (2) In the oil immersion test, no significant difference was observed in the changes in mechanical properties between the Examples and Comparative Examples. This suggests that thermal oxidative degradation did not progress in the oil. The slight changes in physical properties are thought to be due to swelling of the cross-linked material caused by the oil components and the various additives contained therein (Table 1). (3) In the combined oil immersion-air heating aging test, the rate of change in elongation at break of Comparative Example 2 was significantly lower than that of each of the Examples and was at a level almost equivalent to that of Comparative Example 1. This is presumably due to the extraction of the antioxidant 4,4'-bis(α,α-dimethylbenzyl)diphenylamine from the cross-linked product by oil immersion. On the other hand, in Examples 5 to 8, the anti-aging component remained in the crosslinked product even after oil immersion, and it is thought that the decrease in the rate of change in elongation at break was minimized due to its heat aging resistance even in the subsequent air heating aging test (Figures 5 and 6). (4) In the air heating aging test, a comparison of the change rate of elongation at break between Example 10 and Comparative Example 3 shows that the cross-linked acrylic rubber copolymerized with the copolymerizable antioxidant (e) is stabilized against thermal oxidative degradation. Furthermore, in the early stages of the test, the decrease in the rate of change in strength at break in Example 10 was gradual compared to Comparative Examples 3 and 4, indicating that softening and deterioration were suppressed. This is presumably due to the crosslinking action of the copolymerizable antioxidant (e) in the acrylic rubber. This result indicates that the copolymerizable antioxidant (e) has a crosslinking action in addition to antiaging properties (Figures 7 and 8). (5) In the combined oil immersion and air heating aging test, the decrease in the rate of change in strength at break in Example 10 was smaller than that in Comparative Examples 3 and 4. This is presumably due to the crosslinking action of the copolymerizable antioxidant (e) component in the acrylic rubber (FIGS. 9 and 10). (6) In the combined air aging-oil immersion-air aging test, the rate of change in elongation at break of Comparative Examples 3 and 4 was significantly lower than that of Example 10. This is presumably due to the extraction of the antioxidant 4,4'-bis(α,α-dimethylbenzyl)diphenylamine from the cross-linked product by oil immersion. Furthermore, in the same composite test, the smaller rate of change in strength at break in Example 10 compared to Comparative Examples 3 and 4 is thought to be due to the crosslinking action of the copolymerizable antioxidant (e) component (FIGS. 11 and 12). (7) These results are believed to be due to the fact that the copolymerizable antioxidant used in the present invention chemically bonds to the rubber molecular chain, thereby suppressing the extraction of the antioxidant by oil immersion. This demonstrates the effectiveness of copolymerizing a copolymerizable antioxidant with an acrylic elastomer copolymer. (8) When an acrylic elastomer copolymer containing compound (e) was used, the decrease in elongation at break was gradual, indicating stabilization against thermal oxidative degradation (Example 12). On the other hand, when compound (b-1) or compound (e) was directly blended with an acrylic elastomer copolymer not containing compound (e) (Comparative Examples 6 and 7), the thermal aging properties were essentially the same as those observed when no antiaging component was blended (Comparative Example 5). This suggests that compound (b-1) and compound (e) themselves do not exhibit thermal aging resistance. In other words, compound (e) itself does not exhibit thermal aging resistance, but when copolymerized with a (meth)acrylate monomer, thermal aging resistance is exerted, resulting in stabilization of the acrylic elastomer copolymer against thermal oxidative degradation. (9) When the crosslinking site monomer is an active chlorine-containing unsaturated monomer, copolymerization of compound (e) stabilizes the acrylic elastomer copolymer against thermal oxidative degradation, as shown in the results of the air heating aging test (Examples 14 and 15). In particular, copolymerization of compound (e) significantly inhibits softening and degradation of the crosslinked acrylic elastomer copolymer in the air heating aging test compared to the conventional antioxidant 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Figures 15 to 18). (10) When the crosslinking site monomer is an active chlorine-containing unsaturated monomer, the results of the heat aging test for Example 18 (amount of compound (e) used during polymerization of the acrylic elastomer copolymer: 0.25 wt%) and Comparative Example 12 (amount of antioxidant 4,4'-bis(α,α-dimethylbenzyl)diphenylamine blended: 2.0 parts by weight) show that the amount of antioxidant component used can be reduced by more than 80%. Furthermore, the heat aging prevention effect is also observed in Example 19 (amount of compound (e) used during polymerization of the acrylic elastomer copolymer: 0.10 wt%), in which the amount of antioxidant component was reduced by 95% compared to Comparative Example 12. (11) Because the uncrosslinked acrylic elastomer copolymer in which compound (e) is copolymerized is itself stabilized against thermal oxidative degradation, the Mooney viscosity hardly changes during the heating test. On the other hand, a significant decrease in Mooney viscosity is observed in the uncrosslinked acrylic elastomer copolymer in which compound (e) is not copolymerized (Tables 6 and 7). The significant decrease in Mooney viscosity suggests that the polymer backbone is cleaved due to thermal oxidative degradation, resulting in a decrease in molecular weight. (12) Even when the amount of compound (e) used during polymerization of the acrylic elastomer copolymer was 0.10 to 0.50 wt % (Examples 25 to 27), the crosslinked product was stabilized against thermal oxidative degradation (FIG. 21). [Industrial Applicability]

[0168] The acrylic elastomer copolymer of the present invention can be effectively used as a material for acrylic elastomer molded parts that can withstand various deterioration environments.

Claims

1. general formula (where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group, A is a direct bond or a divalent organic group, B is a direct bond, an oxygen atom, a sulfur atom, a sulfoxide group or a sulfone group, and x is 0 or 1), an acrylic elastomer copolymer comprising an alkyl (meth)acrylate monomer and / or an alkoxyalkyl (meth)acrylate monomer, and a cross-linking site monomer.

2. In the copolymerizable antioxidant represented by the general formula [I], the divalent organic group is represented by the general formula -(CH 2 ) n O(C=O)- (where n is an integer of 1 to 5) or a group represented by the general formula -NH(C=O)(CH 2 ) n 2. The acrylic elastomer copolymer according to claim 1, wherein the group is O(C═O)— (where n is an integer of 1 to 5).

3. The copolymerizable antioxidant is represented by the general formula (where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, R 2 2. The acrylic elastomer copolymer according to claim 1, wherein R is a hydrogen atom or a methyl group, and A is a direct bond or a divalent organic group.

4. The copolymerizable antioxidant is represented by the general formula (where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group, A is a direct bond or a divalent organic group, and B is a direct bond, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.

5. 5. The acrylic elastomer copolymer according to claim 4, wherein in the general formula [III], B is a sulfur atom, a sulfoxide group or a sulfone group.

6. 2. The acrylic elastomer copolymer according to claim 1, wherein the crosslinking site monomer is an α,β-unsaturated carboxylic acid monomer.

7. 2. The acrylic elastomer copolymer according to claim 1, wherein the crosslinking site monomer is an active chlorine-containing unsaturated monomer.

8. 2. The acrylic elastomer copolymer according to claim 1, wherein the crosslinking site monomer is an epoxy group-containing unsaturated monomer.

9. The acrylic elastomer copolymer according to claim 1, (where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group, A is a direct bond or a divalent organic group, and B is a direct bond, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.

10. A crosslinkable acrylic elastomer copolymer composition obtained by blending the acrylic elastomer copolymer according to claim 6 with a crosslinking agent.

11. A crosslinkable acrylic elastomer copolymer composition obtained by blending the acrylic elastomer copolymer according to claim 7 with a crosslinking agent.

12. A crosslinkable acrylic elastomer copolymer composition obtained by blending the acrylic elastomer copolymer according to claim 8 with a crosslinking agent.

13. The crosslinkable acrylic elastomer copolymer composition according to claim 10, wherein the crosslinking agent is a polyamine compound.

14. 12. The crosslinkable acrylic elastomer copolymer composition according to claim 11, wherein the crosslinking agent is 2,4,6-trimercapto-s-triazine.

15. 12. The crosslinkable acrylic elastomer copolymer composition according to claim 11, wherein the crosslinking agent is a fatty acid alkali metal salt.

16. 13. The crosslinkable acrylic elastomer copolymer composition according to claim 12, wherein the crosslinking agent is an ammonium salt of an organic acid.

17. The crosslinkable acrylic elastomer copolymer composition according to claim 12, wherein the crosslinking agent is a polyamine compound.

Images