Triarylamine compound, antioxidant, rubber composition, and tire

Abstract

The purpose of the present invention is to provide a triarylamine compound which enables a vulcanized rubber to exhibit good weather resistance and exhibit superior workability. Provided is a triarylamine compound.

Description

Triarylamine compound, antioxidant, rubber composition, and tire

[0001] The present invention relates to a triarylamine compound, an antioxidant, a rubber composition, and a tire.

[0002] US Pat. No. 5,629,493 discloses 4,4'-bis(methylamino)triphenylamine as an antiozonant for rubber.

[0003] US Pat. No. 5,649,493 discloses a tire belt comprising a rubber composition based on at least one isoprene elastomer, a reinforcing filler, a crosslinking system, and an antioxidant (4,4'-bis(alkylamino)triphenylamine).

[0004] U.S. Patent US3,277,174 International Publication WO2007 / 121936A1

[0005] An object of the present invention is to provide a triarylamine compound which, when used in vulcanized rubber, has good weather resistance and can exhibit superior processability.

[0006] The present inventors have discovered that a specific triarylamine compound, when used in vulcanized rubber, maintains weather resistance at the same level as conventional triarylamine compounds (Patent Document 2) and has superior processability.

[0007] The present inventors have further investigated based on this finding and have completed the present invention. The present invention encompasses the following triarylamine compounds.

[0008] Item 1. A triarylamine compound represented by formula (1). [In formula (1), R 1 , R 2 , and R 3 and each independently represent an alkyl group having 1 to 20 carbon atoms. In formula (1), the alkyl group may have one or more substituents.]

[0009] Item 2. The triarylamine compound according to Item 1, wherein the compound represented by formula (1) is a compound represented by formula (2). [In formula (2), R 1represents an alkyl group having 1 to 8 carbon atoms. 4 , R 5 , R 6 , and R 7 and each independently represent an alkyl group having 1 to 8 carbon atoms. In formula (2), the alkyl group may have one or more substituents. In formula (2), R 4 and R 5 may be bonded to form a ring. 6 and R 7 may be bonded to form a ring.

[0010] Item 3. The triarylamine compound represented by the formula (1) includes N4-isopropyl-N1-[4-(isopropylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine, N4-(1,3-dimethylbutyl)-N1-[4-(1,3-dimethylbutylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine, N1-(4-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-(4-ethoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-(3-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, Item 1. The triarylamine compound according to item 1, which is at least one triarylamine compound selected from the group consisting of N1-(2-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-(1-ethylpropyl)-N4-[4-(1-ethylpropylamino)phenyl]-N4-(4-methoxyphenyl)benzene-1,4-diamine, N1-(4-methoxyphenyl)-N4-1-methylpropyl-N1-[4-(1-methylpropylamino)phenyl]benzene-1,4-diamine, and N1-(4-methoxyphenyl)-N4-(1-propylbutyl)-N1-[4-(1-propylbutylamino)phenyl]benzene-1,4-diamine.

[0011] Item 4. An antioxidant comprising the triarylamine compound according to any one of Items 1 to 3.

[0012] Item 5. A rubber composition comprising a rubber component and the triarylamine compound according to any one of Items 1 to 3.

[0013] Item 6. The rubber composition according to Item 5, comprising 0.2 to 10 parts by mass of the triarylamine compound per 100 parts by mass of the rubber component.

[0014] Item 7. The rubber composition according to Item 5, wherein the rubber component is at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, and butadiene rubber.

[0015] Item 8. A vulcanized rubber comprising a rubber component and the triarylamine compound according to any one of Items 1 to 3.

[0016] Item 9. The vulcanized rubber according to Item 8, containing 0.2 to 10 parts by mass of the triarylamine compound per 100 parts by mass of the rubber component.

[0017] Item 10. The vulcanized rubber according to Item 8, wherein the rubber component is at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, and butadiene rubber.

[0018] Item 11. A tire, a rubber crawler, or a seismic isolation rubber comprising the rubber composition according to Item 5 or the vulcanized rubber according to any one of Items 8 to 10.

[0019] Item 12. A tire component comprising the rubber composition according to Item 5 or the vulcanized rubber according to any one of Items 8 to 10.

[0020] Item 13. The tire component according to Item 12, wherein the tire component is at least one tire component of a tread and a sidewall.

[0021] Item 14. A tire including the tire component according to Item 12 or 13.

[0022] Item 15. A method for preventing aging of vulcanized rubber by blending the triarylamine compound according to any one of items 1 to 3 into vulcanized rubber.

[0023] Item 16. A method for producing a rubber composition, comprising: (1) mixing a rubber component with the triarylamine compound according to any one of Items 1 to 3.

[0024] The triarylamine compound of the present invention exhibits good weather resistance and excellent processability in vulcanized rubber, and is useful as an antioxidant for rubber.

[0025] When the rubber composition (vulcanized rubber) containing the triarylamine compound of the present invention is applied to tire components such as treads and sidewalls, it can be processed well, and the produced tires exhibit good weather resistance.

[0026] The present invention can provide a triarylamine compound that can exhibit good weather resistance and superior processability in vulcanized rubber.

[0027] The triarylamine compound of the present invention is useful as an antioxidant for rubber.

[0028] The present invention will be described in detail below. The embodiments of the present invention are intended to provide a better understanding of the gist of the invention, and unless otherwise specified, do not limit the content of the invention.

[0029] In this specification, the terms "comprise" and "contain" are concepts that encompass all of "comprise," "consist essentially of," and "consist only of."

[0030] In this specification, when a numerical range is expressed as "A to B," it means "A or more, and B or less."

[0031] In this specification, when the terms "parts," "%," and the like are used, they generally represent parts by mass, parts by weight, mass % (wt%), or weight % (wt%).

[0032] [1] Triarylamine Compound Represented by Formula (1) The present invention includes a triarylamine compound represented by formula (1).

[0033]

[0034] In formula (1), R 1 , R 2 , and R 3 and each independently represent an alkyl group having 1 to 20 carbon atoms. In formula (1), the alkyl group may have one or more substituents.

[0035] The alkyl group is not particularly limited, and is preferably a linear, branched, or cyclic alkyl group.

[0036] The alkyl group is preferably, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-methylpropyl, 1-ethylpropyl, 2-ethylpropyl, n-pentyl, 1-methylbutyl, s-pentyl, isopentyl, neopentyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, isohexyl, 1-isopropyl-2-methylpropyl, 1-propylbutyl, 1,4-dimethylpentyl, 3-methylpentyl, n-heptyl, 1-methylhexyl, 1-methylheptyl, n-octyl, 1-isobutyl-3-methylbutyl. and linear or branched alkyl groups having 1 to 20 carbon atoms, such as 1-ethyl-3-methylpentyl, n-nonyl, 1-methyloctyl, n-decyl, 1-methylnosyl, n-undecyl, 1-methyldecyl, n-dodecyl, 1-methyldecyl, 5-propylnonyl, n-tridecyl, 1-methyldodecyl, n-tetradecyl, 1-methyltridecyl, n-pentadecyl, 1-methyltetradecyl, hexadecyl, 1-methylpentadecyl, heptadecyl, 1-methylhexadecyl, octadecyl, 1-methylheptadecyl, nonadecyl, 1-methyloctadecyl, eicosyl, and 1-methylnonadecyl.

[0037] The alkyl group is preferably a cyclic alkyl group having 3 to 10 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonosyl, cyclodecyl, and the like.

[0038] More preferably, the alkyl group is a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-methylpropyl, 1-ethylpropyl, n-pentyl, 1-methylbutyl, s-pentyl, isopentyl, neopentyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, isohexyl, 1-isopropyl-2-methylpropyl, 1-propylbutyl, 1,4-dimethylpentyl, 3-methylpentyl, n-heptyl, 1-methylhexyl, 1-methylheptyl, n-octyl, 1-isobutyl-3-methylbutyl, 1-ethyl-3-methylpentyl, n-nonyl, 1-methyloctyl, n-decyl, or 1-methylnosyl.

[0039] The triarylamine compound represented by formula (1) is preferably R 1 is a linear or branched alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc., and more preferably, R 1 is a methyl or ethyl group, and particularly preferred are compounds in which R 1 is a methyl group.

[0040] OR on the phenyl group in formula (1) 1 The substitution position of OR on the phenyl group in formula (1) is not particularly limited. 1 The substitution position of is preferably OR at the 4-position (para position) relative to the bonding position of the nitrogen atom of the phenyl group. 1 It is a compound having the formula:

[0041] The triarylamine compound represented by formula (1) is preferably R 2 and R 3are the same and are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-methylpropyl, 1-ethylpropyl, 2-ethylpropyl, n-pentyl, 1-methylbutyl, s-pentyl, isopentyl, neopentyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, isohexyl, 1-isopropyl-2-methylpropyl, 1-propylbutyl, 1,4-dimethylpentyl, 3-methylpentyl, n-heptyl, 1-methylhexyl, 1-methylheptyl, n-octyl, 1-isobutyl-3-methylbutyl, 1-ethyl-3 and compounds which are linear or branched alkyl groups having 1 to 20 carbon atoms, such as 1-methylpentyl, n-nonyl, 1-methyloctyl, n-decyl, 1-methylnosyl, n-undecyl, 1-methyldecyl, n-dodecyl, 1-methyldecyl, 5-propylnonyl, n-tridecyl, 1-methyldodecyl, n-tetradecyl, 1-methyltridecyl, n-pentadecyl, 1-methyltetradecyl, hexadecyl, 1-methylpentadecyl, heptadecyl, 1-methylhexadecyl, octadecyl, 1-methylheptadecyl, nonadecyl, 1-methyloctadecyl, eicosyl, and 1-methylnonadecyl.

[0042] The triarylamine compound represented by formula (1) is more preferably R 2 and R 3 are the same and are linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-methylpropyl, 1-ethylpropyl, n-pentyl, 1-methylbutyl, s-pentyl, isopentyl, neopentyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, isohexyl, 1-isopropyl-2-methylpropyl, 1-propylbutyl, 1,4-dimethylpentyl, 3-methylpentyl, n-heptyl, 1-methylhexyl, 1-methylheptyl, n-octyl, 1-isobutyl-3-methylbutyl, 1-ethyl-3-methylpentyl, n-nonyl, 1-methyloctyl, n-decyl, or 1-methylnosyl.

[0043] The triarylamine compound represented by formula (1) is more preferably R 2 and R 3 are the same and are isopropyl, 1,3-dimethylbutyl, 1-ethylpropyl, 1-propylbutyl, 1-methylpropyl, or 1-methylheptyl.

[0044] The triarylamine compound represented by formula (1) is preferably R 1 is a linear or branched alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, or isopropyl; R 2 and R 3 are the same and are linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-methylpropyl, 1-ethylpropyl, n-pentyl, 1-methylbutyl, s-pentyl, isopentyl, neopentyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, isohexyl, 1-isopropyl-2-methylpropyl, 1-propylbutyl, 1,4-dimethylpentyl, 3-methylpentyl, n-heptyl, 1-methylhexyl, 1-methylheptyl, n-octyl, 1-isobutyl-3-methylbutyl, 1-ethyl-3-methylpentyl, n-nonyl, 1-methyloctyl, n-decyl, or 1-methylnosyl.

[0045] These alkyl groups may each have one or more substituents at any substitutable position. There are no particular limitations on the "substituents."

[0046] The "substituent" is preferably a halogen atom, an amino group, an aminoalkyl group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a carboxyl group, a carboxyalkyl group, a formyl group, a nitrile group, a nitro group, an alkyl group, a hydroxyalkyl group, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a thiol group, an alkylthio group, an arylthio group, or the like.

[0047] The number of "substituents" is preferably 1 to 5, and more preferably 1 to 3.

[0048] The "halogen atom" is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and more preferably a chlorine atom, a bromine atom, an iodine atom, etc.

[0049] The "amino group" is not only an amino group represented by -NH2, but also preferably a linear or branched monoalkylamino group such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino, or 3-methylpentylamino.

[0050] The "amino group" is preferably a substituted amino group such as a dialkylamino group having two linear or branched alkyl groups, such as a dimethylamino, ethylmethylamino, or diethylamino group.

[0051] The "aminoalkyl group" is preferably an aminoalkyl group such as aminomethyl, methylaminomethyl, ethylaminomethyl, dimethylaminomethyl, ethylmethylaminomethyl, diethylaminomethyl, 2-aminoethyl, 2-(methylamino)ethyl, 2-(ethylamino)ethyl, 2-(dimethylamino)ethyl, 2-(ethylmethylamino)ethyl, 2-(diethylamino)ethyl, 3-aminopropyl, 3-(methylamino)propyl, 3-(ethylamino)propyl, 3-(dimethylamino)propyl, 3-(ethylmethylamino)propyl, or 3-(diethylamino)propyl group, a monoalkyl-substituted aminoalkyl group, or a dialkyl-substituted aminoalkyl group.

[0052] The "alkoxycarbonyl group" is preferably a methoxycarbonyl group, an ethoxycarbonyl group, or the like.

[0053] The "acyl group" is preferably a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms, such as acetyl, propionyl, or pivaloyl.

[0054] The "acyloxy group" is preferably an acetyloxy group, a propionyloxy group, an n-butyryloxy group, or the like.

[0055] The "amide group" is preferably a carboxylic acid amide group such as acetamide or benzamide. The "amide group" is preferably a thioamide group such as thioacetamide or thiobenzamide. The "amide group" is preferably an N-substituted amide group such as N-methylacetamide or N-benzylacetamide.

[0056] The "carboxyalkyl group" is preferably a carboxyalkyl group such as carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl, carboxy-n-pentyl, or carboxy-n-hexyl.

[0057] The "hydroxyalkyl group" is preferably a hydroxy-alkyl group such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, or hydroxy-n-butyl.

[0058] The "alkoxy group" is preferably a linear, branched, or cyclic alkoxy group. The "alkoxy group" is preferably a linear or branched alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, n-pentyloxy, neopentyloxy, or n-hexyloxy. The "alkoxy group" is preferably a cyclic alkoxy group such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, or cyclooctyloxy.

[0059] The "aryl group" is preferably a phenyl, biphenyl, naphthyl, dihydroindenyl, 9H-fluorenyl group, or the like.

[0060] The "aryloxy group" is preferably a phenoxy group, a biphenyloxy group, a naphthoxy group, or the like.

[0061] The "heterocyclic group" is preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 3-pyridazyl, 4-pyridazyl, or the like.

[0062] The "heterocyclic group" is preferably 4-(1,2,3-triazyl), 5-(1,2,3-triazyl), 2-(1,3,5-triazyl), 3-(1,2,4-triazyl), 5-(1,2,4-triazyl), 6-(1,2,4-triazyl), or the like.

[0063] The "heterocyclic group" is preferably 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 7-quinoxalyl, 8-quinoxalyl, 3-cinnolyl, 4-cinnolyl, 5-cinnolyl, 6-cinnolyl, 7-cinnolyl, 8-cinnolyl, 2-quinazolyl, 4-quinazolyl, 5-quinazolyl, 6-quinazolyl, 7-quinazolyl, 8-quinazolyl, and the like.

[0064] The "heterocyclic group" is preferably 1-phthalazyl, 4-phthalazyl, 5-phthalazyl, 6-phthalazyl, 7-phthalazyl, 8-phthalazyl, 1-tetrahydroquinolyl, 2-tetrahydroquinolyl, 3-tetrahydroquinolyl, 4-tetrahydroquinolyl, 5-tetrahydroquinolyl, 6-tetrahydroquinolyl, 7-tetrahydroquinolyl, 8-tetrahydroquinolyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, and the like.

[0065] The "heterocyclic group" is preferably 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 4-(1,2,3-thiadiazolyl), 5-(1,2,3-thiadiazolyl), 3-(1,2,5-thiadiazolyl), 2-(1,3,4-thiadiazolyl), 4-(1,2,3-oxadiazolyl), 5-(1,2,3-oxadiazolyl), 3-(1,2,4-oxadiazolyl), 5-(1,2,4-oxadiazolyl), 3-(1,2,5-oxadiazolyl), 2-(1,3,4-oxadiazolyl), and the like.

[0066] The "heterocyclic group" is preferably 1-(1,2,3-triazolyl), 4-(1,2,3-triazolyl), 5-(1,2,3-triazolyl), 1-(1,2,4-triazolyl), 3-(1,2,4-triazolyl), 5-(1,2,4-triazolyl), or the like.

[0067] The "heterocyclic group" is preferably 1-tetrazolyl, 5-tetrazolyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, or the like.

[0068] The "heterocyclic group" is preferably 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, or the like.

[0069] The "heterocyclic group" is preferably 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, or the like.

[0070] The "heterocyclic group" is preferably 2-benzothienyl, 3-benzothienyl, 4-benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, 1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl, or the like.

[0071] The "heterocyclic group" is preferably 2-morpholyl, 3-morpholyl, 4-morpholyl, 1-piperazyl, 2-piperazyl, 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, and the like.

[0072] Preferred examples of the "heterocyclic group" include furanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 5-methyl-3-oxo-2,3-dihydro-1H-pyrazol-4-yl, and the like.

[0073] The triarylamine compound of the present invention is preferably a triarylamine compound represented by formula (2).

[0074]

[0075] In formula (2), R 1 represents an alkyl group having 1 to 8 carbon atoms. In formula (2), the alkyl group may have one or more substituents. In formula (2), R 4 , R 5 , R 6 , and R 7 Each of R independently represents an alkyl group having 1 to 8 carbon atoms. 4 and R 5 may be bonded to form a ring.6 and R 7 may be bonded to form a ring.

[0076] The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, 2-methylpropyl, 2-methylbutyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, etc.

[0077] R 4 and R 5 When R and R are bonded to form a ring, 6 and R 7 When these groups combine to form a ring, they preferably form a cyclic alkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0078] Among the triarylamine compounds represented by formula (2), preferably, R 1 is a linear or branched alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc., and more preferably, R 1 is a methyl or ethyl group, and particularly preferred are compounds in which R 1 is a methyl group.

[0079] OR on the phenyl group in formula (2) 1 The substitution position of OR on the phenyl group in formula (2) is not particularly limited. 1 The substitution position of is preferably at the 4-position (para position) relative to the bonding position of the nitrogen atom of the phenyl group, and 1 It is a compound having the formula:

[0080] The triarylamine compound represented by formula (2) is preferably R 4 , R 5 , R 6 , and R 7are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, 2-methylpropyl, 2-methylbutyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, or n-octyl.

[0081] The triarylamine compound represented by formula (2) is more preferably R 4 , R 5 , R 6 , and R 7 are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, 2-methylpropyl, 2-methylbutyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, or n-heptyl.

[0082] The triarylamine compound represented by formula (2) is more preferably R 4 , R 5 , R 6 , and R 7 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, 2-methylpropyl, 2-methylbutyl, isopentyl, neopentyl, n-hexyl, isohexyl, or 3-methylpentyl.

[0083] The triarylamine compound represented by formula (2) is preferably R 1 is a linear or branched alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, or isopropyl; R 4 , R 5 , R 6 , and R 7are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, 2-methylpropyl, 2-methylbutyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, or n-octyl.

[0084] These alkyl groups may have one or more substituents at any substitutable position. There are no particular limitations on the "substituents."

[0085] The "substituent" is preferably a halogen atom, an amino group, an aminoalkyl group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a carboxyl group, a carboxyalkyl group, a formyl group, a nitrile group, a nitro group, an alkyl group, a hydroxyalkyl group, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a thiol group, an alkylthio group, an arylthio group, or the like.

[0086] The number of "substituents" is preferably 1 to 5, and more preferably 1 to 3.

[0087] Other explanations for the "substituent" are as described above.

[0088] The triarylamine compound of the present invention is preferably at least one triarylamine compound selected from the group consisting of the following compounds:

[0089] N4-Isopropyl-N1-[4-(isopropylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine

[0090] N4-(1,3-dimethylbutyl)-N1-[4-(1,3-dimethylbutylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine

[0091] N1-(4-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine

[0092] N1-(4-ethoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine

[0093] N1-(3-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine

[0094] N1-(2-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine

[0095] N1-(1-ethylpropyl)-N4-[4-(1-ethylpropylamino)phenyl]-N4-(4-methoxyphenyl)benzene-1,4-diamine

[0096] N1-(4-methoxyphenyl)-N4-1-methylpropyl-N1-[4-(1-methylpropylamino)phenyl]benzene-1,4-diamine

[0097] N1-(4-methoxyphenyl)-N4-(1-propylbutyl)-N1-[4-(1-propylbutylamino)phenyl]benzene-1,4-diamine

[0098] [2] Antiaging Agent The present invention encompasses an antioxidant containing the triarylamine compound of the present invention represented by formula (1). The triarylamine compound of the present invention is useful as an antioxidant for rubber.

[0099] [3] Rubber Composition The present invention encompasses a rubber composition containing a rubber component and the triarylamine compound represented by formula (1) of the present invention.

[0100] The triarylamine compound of the present invention has a specific structure, and in vulcanized rubber, compared with conventional triarylamine compounds (Patent Document 2), it maintains weather resistance to the same degree and has better processability.

[0101] The triarylamine compound of the present invention reacts with an oxidizing agent such as ozone before the rubber component reacts with the triarylamine compound of the present invention. The compound produced by further oxidation of the triarylamine compound of the present invention is stable and does not react with rubber, etc., and therefore, rubber degradation can be suppressed.

[0102] [3-1] Rubber Component The rubber composition of the present invention contains a rubber component.

[0103] The rubber component is not particularly limited, and is preferably a polymer containing conjugated diene units and / or olefin units, more preferably natural rubber (NR), synthetic diene rubber, a mixture of natural rubber and synthetic diene rubber, or other non-diene rubber.

[0104] The natural rubber (NR) is preferably natural rubber latex, technically graded rubber (TSR), smoked sheet rubber (RSS), gutta percha, eucommia-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, or the like.

[0105] Natural rubber (NR) includes modified natural rubber and modified natural rubber obtained by modifying the natural rubber. Examples of modified natural rubber include epoxidized natural rubber, methacrylic acid-modified natural rubber, and styrene-modified natural rubber. Examples of modified natural rubber include highly purified natural rubber.

[0106] The synthetic diene rubber is preferably a styrene-butadiene copolymer rubber (SBR), a butadiene rubber (BR), an isoprene rubber (IR), a nitrile rubber (NBR), a chloroprene rubber (CR), an ethylene-propylene-diene terpolymer rubber (EPDM), a styrene-isoprene-styrene triblock copolymer (SIS), a styrene-butadiene-styrene triblock copolymer (SBS), or the like.

[0107] The synthetic diene rubber includes a modified synthetic diene rubber obtained by modifying the synthetic diene rubber. The modified synthetic diene rubber preferably includes a diene rubber modified by a modification method such as main chain modification, single-end modification, or both-end modification. The modified functional group of the modified synthetic diene rubber is preferably an epoxy group, an amino group, an alkoxysilyl group, a hydroxyl group, or other functional group, and one or more of these functional groups may be contained in the modified synthetic diene rubber.

[0108] The method for producing the synthetic diene rubber is not particularly limited. The method for producing the synthetic diene rubber is preferably emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, cationic polymerization, etc. The glass transition temperature of the synthetic diene rubber is not particularly limited.

[0109] There are no particular limitations on the cis / trans / vinyl ratio of the double bonds of the natural rubber and synthetic diene rubber, and any ratio can be suitably used.

[0110] The number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited. The number average molecular weight of the diene rubber is preferably about 500 to 3,000,000, and the molecular weight distribution is preferably about 1.5 to 15.

[0111] The rubber component may be one of these rubber components or a mixture (blend) of two or more of them.

[0112] The rubber composition preferably contains, as a rubber component, at least one rubber component selected from the group consisting of the above-mentioned rubber components, more preferably at least one rubber component selected from the group consisting of NR, IR, SBR, EPDM, and BR, even more preferably at least one rubber component selected from the group consisting of NR, IR, SBR, and BR, and particularly preferably at least one rubber component selected from the group consisting of NR and IR.

[0113] There are no particular limitations on the blend ratio of the rubber components in the rubber composition, but the blend ratio of the rubber components is preferably 50 to 100 parts by mass, more preferably 75 to 100 parts by mass, of at least one rubber component (a mixture of two or more types) selected from the group consisting of NR and IR per 100 parts by mass of the rubber components.

[0114] [3-2] Triarylamine Compound The rubber composition of the present invention contains the triarylamine compound represented by formula (1) of the present invention.

[0115] The rubber composition contains, per 100 parts by mass of the rubber component, preferably 0.2 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, even more preferably 1 part by mass to 10 parts by mass, and particularly preferably 1 part by mass to 8 parts by mass of the triarylamine compound represented by Formula (1).

[0116] The triarylamine compound of the present invention reacts with an oxidizing agent such as ozone before the rubber component reacts with the triarylamine compound of the present invention. The compound produced by further oxidation of the triarylamine compound of the present invention is stable and does not react with rubber, etc., and therefore, rubber degradation can be suppressed.

[0117] The triarylamine compound of the present invention has a specific structure, and in vulcanized rubber, compared with conventional triarylamine compounds (Patent Document 2), it maintains weather resistance to the same degree and has better processability.

[0118] [3-3] Carbon Black and / or Inorganic Filler The rubber composition of the present invention preferably further contains carbon black and / or an inorganic filler. In this specification, the inorganic filler does not include carbon black.

[0119] Carbon black is used to improve the reinforcing properties of rubber. By including carbon black in the rubber component, it is possible to lower the electrical resistance of the rubber, suppress static electricity, and further improve the strength of the rubber.

[0120] The carbon black is not particularly limited, and examples of the carbon black include commercially available carbon black and carbon-silica dual phase filler.

[0121] The carbon black is preferably a high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade carbon black, etc. The carbon black is preferably a SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, FEF grade carbon black.

[0122] The DBP absorption range of the carbon black is preferably 60 cm 3 / 100g~200cm 3 / 100g, more preferably 70cm 3 / 100g~180cm 3 / 100g, particularly preferably 80cm 3 / 100g~160cm 3 / 100g.

[0123] The nitrogen adsorption specific surface area (N2SA) of carbon black is measured in accordance with JIS K6217-2:2001. The nitrogen adsorption specific surface area of ​​carbon black is preferably in the range of 30 m 2 / g~200m 2 / g, more preferably 40m 2 / g~180m 2 / g, and particularly preferably 50m 2 / g~160m 2 / g.

[0124] Inorganic Filler There are no particular limitations on the inorganic filler, and inorganic compounds commonly used in the rubber industry can be used as the inorganic filler.

[0125] The inorganic compound is preferably silica. The inorganic compound is preferably alumina (Al2O3) such as γ-alumina or α-alumina. The inorganic compound is preferably alumina monohydrate (Al2O3.H2O) such as boehmite or diaspore. The inorganic compound is preferably aluminum hydroxide [Al(OH)3] such as gibbsite or bayerite. The inorganic compound is preferably a crystalline aluminosilicate containing hydrogen, alkali metal, or alkaline earth metal to compensate for the charge, such as various zeolites.

[0126] The inorganic compound is preferably aluminum carbonate [Al2(CO3)3], magnesium hydroxide [Mg(OH)2], magnesium oxide (MgO), magnesium carbonate (MgCO3), talc (3MgO.4SiO2.H2O), attapulgite (5MgO.8SiO2.9H2O), titanium white (TiO2), titanium black (TiO 2n-1 ), calcium oxide (CaO), calcium hydroxide [Ca(OH)2], aluminum magnesium oxide (MgO·Al2O3), clay (Al2O3·2SiO2), kaolin (Al2O3·2SiO2·2H2O), pyrophyllite (Al2O3·4SiO2·H2O), bentonite (Al2O3·4SiO2·2H2O), aluminum silicate (Al2SiO5, Al4·3SiO4·5H2O, etc.), magnesium silicate (Mg2SiO4, MgSiO3, etc.), calcium silicate (Ca2·SiO4, etc.), aluminum calcium silicate (Al2O3·CaO·2SiO2, etc.), magnesium calcium silicate (CaMgSiO4), calcium carbonate (CaCO3), zirconium oxide (ZrO2), zirconium hydroxide [ZrO(OH)2·nH2O], zirconium carbonate [Zr(CO3)2], zinc acrylate, zinc methacrylate, etc.

[0127] The inorganic filler may preferably be an inorganic compound whose surface has been organically treated in order to improve its affinity with the rubber component.

[0128] The inorganic filler is preferably silica from the viewpoint of being able to impart rubber strength. The silica is preferably wet silica, dry silica, or colloidal silica, more preferably wet silica. The silica may preferably have its surface organically treated to improve affinity with the rubber component.

[0129] The BET specific surface area of ​​silica is measured in accordance with ISO 5794 / 1. The range of the BET specific surface area of ​​silica is preferably 40 m 2 / g~350m 2 / g. Silica having a BET specific surface area in this range has the advantage of being able to achieve both rubber reinforcement and dispersibility in the rubber component. The BET specific surface area of ​​the silica is more preferably 80 m 2 / g~300m 2 / g, more preferably 100m 2 / g~270m 2 / g, and particularly preferably 110m 2 / g~270m 2 / g.

[0130] Commercially available silica products include, for example, the product name "HD165MP" (BET specific surface area = 165 m) manufactured by Quechen Silicon Chemical Co., Ltd. 2 / g), "HD115MP" (BET specific surface area = 115m 2 / g), "HD200MP" (BET specific surface area = 200m 2 / g), "HD250MP" (BET specific surface area = 250m 2 / g), and Tosoh Silica Corporation's product name "Nipsil AQ" (BET specific surface area = 205 m 2 / g), "Nipsil KQ" (BET specific surface area = 240 m 2 / g), and Ultrasil VN3 (BET specific surface area = 175 m) manufactured by Degussa. 2 / g), etc.

[0131] The carbon black and / or inorganic filler may be used alone or in combination (blended) of two or more kinds.

[0132] The rubber composition of the present invention preferably contains 10 to 150 parts by mass of carbon black and / or inorganic filler per 100 parts by mass of the rubber component, more preferably 15 to 100 parts by mass, and even more preferably 30 to 80 parts by mass. When both carbon black and inorganic filler are compounded, the total amount of both components may be appropriately adjusted so that it falls within the above range.

[0133] The amount of carbon black and / or inorganic filler to be compounded is preferably 30 parts by mass or more per 100 parts by mass of the rubber component from the viewpoint of improving the reinforcement of the rubber composition, and is preferably 80 parts by mass or less from the viewpoint of improving the tear strength.

[0134] The amount of carbon black added is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, per 100 parts by mass of the rubber component. The amount of carbon black added is preferably 10 parts by mass or more from the viewpoint of ensuring antistatic performance and rubber strength performance, and is preferably 60 parts by mass or less from the viewpoint of improving tear strength.

[0135] The blending amount of the inorganic filler (such as silica) is preferably 10 parts by mass to 200 parts by mass, more preferably 30 parts by mass to 130 parts by mass, and even more preferably 35 parts by mass to 100 parts by mass, per 100 parts by mass of the rubber component.

[0136] Silane Coupling Agents, etc. When the rubber composition of the present invention contains an inorganic filler such as carbon black or silica, a silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconate coupling agent, etc. may be compounded into the rubber composition for the purpose of further increasing the reinforcing properties of the rubber composition by the carbon black, silica, etc., and for the purpose of further increasing the tear strength and abrasion resistance of the rubber composition.

[0137] The silane coupling agent is preferably a sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, alkyl-based or other silane coupling agent.

[0138] Examples of sulfide-based silane coupling agents include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-methyldimethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(3-methyldimethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-methyldimethoxysilylpropyl)trisulfide, and bis(3-methyldimethoxysilylpropyl). ) trisulfide, bis(2-triethoxysilylethyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) tetrasulfide, bis(3-monoethoxydimethylsilylpropyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(3-monomethoxydimethylsilylpropyl) tetrasulfide, bis(3-monomethoxydimethylsilylpropyl) trisulfide, bis(3-monomethoxydimethylsilylpropyl) disulfide, bis(2-monoethoxydimethylsilylethyl) tetrasulfide, bis(2-monoethoxydimethylsilylethyl) trisulfide, bis(2-monoethoxydimethylsilylethyl) disulfide, etc. Of these, bis(3-triethoxysilylpropyl) tetrasulfide is particularly preferred.

[0139] Examples of thioester-based silane coupling agents include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, and 2-lauroylthioethyltrimethoxysilane.

[0140] Examples of thiol-based silane coupling agents include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-[ethoxybis(3,6,9,12,15-pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol.

[0141] Examples of olefin-based silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxysilane, 3-(methoxydimethoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, and 3-[tris(trimethylsiloxy)silyl]propyl methacrylate.

[0142] Examples of epoxy-based silane coupling agents include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, triethoxy(3-glycidyloxypropyl)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Of these, 3-glycidyloxypropyltrimethoxysilane is preferred.

[0143] Examples of amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Of these, 3-aminopropyltriethoxysilane is preferred.

[0144] Examples of alkyl-based silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, etc. Of these, methyltriethoxysilane is preferred.

[0145] Among these silane coupling agents, bis(3-triethoxysilylpropyl)tetrasulfide is particularly preferred.

[0146] The titanate coupling agent is preferably an alkoxide-based, chelate-based, or acylate-based titanate coupling agent.

[0147] Examples of alkoxide-based titanate coupling agents include tetraisopropyl titanate, tetra-normal-butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetra-tertiary-butyl titanate, tetrastearyl titanate, etc. Among these, tetraisopropyl titanate is preferred.

[0148] Examples of chelate titanate coupling agents include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium dodecylbenzenesulfonate compounds, titanium phosphate compounds, titanium octylene glycolate, titanium ethylacetoacetate, titanium lactate ammonium salt, titanium lactate, titanium ethanolaminate, titanium octylene glycolate, titanium aminoethylaminoethanolate, etc. Of these, titanium acetylacetonate is preferred.

[0149] Examples of acylate-based titanate coupling agents include titanium isostearate.

[0150] The aluminate coupling agent is not particularly limited, and commercially available products can be suitably used. Examples of such aluminate coupling agents include 9-octadecenylacetoacetate aluminum diisopropylate, aluminum sec-butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum trisethylacetoacetate. Of these, 9-octadecenylacetoacetate aluminum diisopropylate is preferred.

[0151] The zirconate coupling agent is preferably an alkoxide-based, chelate-based, or acylate-based zirconate coupling agent.

[0152] Examples of the alkoxide-based zirconate coupling agent include normal propyl zirconate, normal butyl zirconate, etc. Among these, normal butyl zirconate is preferred.

[0153] Examples of chelate-based zirconate coupling agents include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetoacetate, zirconium lactate ammonium salt, etc. Among these, zirconium tetraacetylacetonate is preferred.

[0154] Examples of acylate-based zirconate coupling agents include zirconium stearate, zirconium octylate, etc. Among these, zirconium stearate is preferred.

[0155] The silane coupling agent, titanate coupling agent, aluminate coupling agent, or zirconate coupling agent may be used alone or in combination (blended) of two or more.

[0156] In the rubber composition of the present invention, the blending amount of the silane coupling agent, titanate coupling agent, aluminate coupling agent, or zirconate coupling agent is preferably 0.1 to 20 parts by mass, more preferably 3 to 15 parts by mass, per 100 parts by mass of carbon black and / or inorganic filler. By setting the blending amount of the silane coupling agent, titanate coupling agent, aluminate coupling agent, or zirconate coupling agent to 0.1 part by mass or more per 100 parts by mass of carbon black and / or inorganic filler, the effect of improving the tear strength of the rubber composition can be more suitably exhibited, and by setting the blending amount to 20 parts by mass or less, the cost of the rubber composition can be reduced, improving economy.

[0157] [3-4] Other Compounding Agents The rubber composition of the present invention may contain, in addition to the rubber component, the triarylamine compound represented by formula (1) of the present invention, and, as necessary, carbon black and / or an inorganic filler, compounding agents commonly used in the rubber industry, which may be appropriately selected and compounded.

[0158] Examples of the compounding agents include antioxidants other than the triarylamine compound of the present invention, softeners, processing aids, waxes, resins, foaming agents, oils, zinc oxide (ZnO), stearic acid, vulcanization accelerators, vulcanization retarders, vulcanizing agents (sulfur, etc.), crosslinking agents, etc.

[0159] The triarylamine compound of the present invention may be used in combination with an antioxidant other than the triarylamine compound of the present invention. Examples of antioxidants other than the triarylamine compound of the present invention include aromatic secondary amine antioxidants, amine-ketone antioxidants, monophenol antioxidants, bisphenol antioxidants, polyphenol antioxidants, benzimidazole antioxidants, dithiocarbamic acid antioxidants, thiourea antioxidants, phosphorous acid antioxidants, organic thioacid antioxidants, sulfide antioxidants, special wax antioxidants, and triarylamine antioxidants other than the triarylamine compound of the present invention.

[0160] Examples of aromatic secondary amine antioxidants include N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamido)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)N'-phenyl-p-phenylenediamine, and N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine.

[0161] Examples of the amine-ketone antioxidant include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and a reaction product of diphenylamine and acetone.

[0162] Examples of the monophenol-based antioxidant include 2,6-di-tert-butyl-4-methylphenol, mono(α-methylbenzyl)phenol, di(α-methylbenzyl)phenol, and tri(α-methylbenzyl)phenol.

[0163] Examples of bisphenol-based antioxidants include 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), and butylated reaction products of p-cresol and dicyclopentadiene.

[0164] Examples of polyphenol-based antioxidants include 2,5-di-tert-butylhydroquinone and 2,5-di-tert-amylhydroquinone.

[0165] Examples of the benzimidazole antioxidant include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts of 2-mercaptobenzimidazole.

[0166] Examples of dithiocarbamate antioxidants include nickel dibutyldithiocarbamate.

[0167] Examples of the thiourea-based antioxidant include 1,3-bis(dimethylaminopropyl)-2-thiourea and tributylthiourea.

[0168] Examples of the phosphorous acid-based antioxidant include tris(nonylphenyl)phosphite.

[0169] Examples of the organic thioacid-based antiaging agent include dilauryl thiodipropionate.

[0170] Examples of sulfide-based antioxidants include bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide.

[0171] The triarylamine-based antioxidant other than the triarylamine compound of the present invention is preferably N1-phenyl-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-phenyl-N4-(1-methylpropyl)-N1-[4-(1-methylpropylamino)phenyl]benzene-1,4-diamine, N1-phenyl-N4-(1-propylbutyl)-N1-[4-(1-propylbutylamino)phenyl]benzene-1,4-diamine, N1-phenyl-N4-(1-ethylbutyl)-N1-[4-(1-ethylbutylamino)phenyl]benzene-1,4-diamine, N1-phenyl-N4-(1-propyl)-N1-[4-(1-ethylpropylamino)phenyl]benzene-1,4-diamine, N1-phenyl-N4-(1-propyl)-N1-[4-(1-propylamino)phenyl]benzene-1,4-diamine, N1-phenyl-N4-(1,3-dimethylbutyl)-N1-[4-(1,3-dimethylbutylamino)phenyl]benzene-1,4-diamine, and N1-phenyl-N4-(1,4-dimethylpentyl)-N1-[4-(1,4-dimethylpentylamino)phenyl]benzene-1,4-diamine.

[0172] The blending amount of the antioxidant other than the triarylamine compound of the present invention is not particularly limited, but is preferably 0 to 10 parts by mass per 100 parts by mass of the rubber component.

[0173] Examples of processing aids include fatty acid metal salts and fatty acid esters.

[0174] Examples of the metal in the fatty acid metal salt include Zn, K, Ca, Na, Mg, Co, Ni, Ba, Fe, Al, Cu, and Mn, with Zn, K, and Ca being preferred.

[0175] The fatty acid of the fatty acid metal salt may be a saturated or unsaturated fatty acid having a straight-chain, branched or cyclic structure and having 4 to 30 carbon atoms, or a mixture thereof. Of these, a saturated or unsaturated straight-chain fatty acid having 10 to 22 carbon atoms is preferred, and examples thereof include capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, linoleic acid, linolenic acid, and arachidonic acid.

[0176] Preferred fatty acid metal salts include zinc stearate, calcium stearate, potassium stearate, zinc laurate, calcium laurate, and potassium laurate.

[0177] The fatty acid metal salt may be used alone or in combination of two or more. The amount of the fatty acid metal salt is not particularly limited, but is preferably 0.2 to 20 parts by mass per 100 parts by mass of the rubber component.

[0178] Examples of fatty acids for the fatty acid ester include saturated or unsaturated fatty acids having a straight-chain, branched or cyclic structure and having 3 to 30 carbon atoms, or mixtures thereof. Among these, saturated or unsaturated straight-chain fatty acids having 10 to 22 carbon atoms are preferred, and examples thereof include capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, linoleic acid, linolenic acid, and arachidonic acid.

[0179] Preferred fatty acid esters include methyl laurate, ethyl laurate, methyl palmitate, ethyl palmitate, methyl stearate, ethyl stearate, methyl oleate, and methyl oleate.

[0180] The fatty acid esters may be used alone or in combination of two or more.

[0181] The amount of the fatty acid ester to be mixed is not particularly limited, but is preferably 0.2 to 20 parts by mass per 100 parts by mass of the rubber component.

[0182] Examples of waxes include paraffin wax, microcrystalline wax, etc. The blending amount is not particularly limited, but it is preferably 0.1 to 5 parts by mass per 100 parts by mass of the rubber component.

[0183] Examples of resins include C ５ based resin, C ５ -C ９ based resin, C ９ Examples of thermoplastic resins include olefin resins, dicyclopentadiene resins, temperphenol resins, terpene resins, rosin resins, and alkylphenol resins.

[0184] C ５ The C-based resin is ５ This refers to synthetic petroleum resins, ５ Examples of the resins include C4 obtained by thermal decomposition of naphtha in the petrochemical industry. ５ The fraction was treated with AlCl ３ , B.F. ３ Examples of the aliphatic petroleum resins include those obtained by polymerization using a Friedel-Crafts catalyst such as the above-mentioned C ５ The fraction usually contains olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene, and diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.

[0185] C ５ -C ９ The C-based resin is ５ -C ９ This refers to synthetic petroleum resins, ５ -C ９ Examples of the resin include petroleum-derived C ５ Fraction and C ９ and a solid polymer obtained by polymerizing the distillate with a Friedel-Crafts catalyst such as AlCl3 or BF3. More specifically, examples thereof include copolymers containing styrene, vinyltoluene, α-methylstyrene, indene, or the like as a main component.

[0186] C ９C-based resins are produced, for example, by-products of petrochemical basic raw materials such as ethylene and propylene during the thermal decomposition of naphtha in the petrochemical industry. ９ It is a resin obtained by polymerizing aromatic compounds with 9 carbon atoms, the main monomers of which are vinyltoluene, alkylstyrene, and indene. ９ Specific examples of the fraction include vinyltoluene, α-methylstyrene, β-methylstyrene, γ-methylstyrene, o-methylstyrene, p-methylstyrene, and indene. ９ The resin is C ９ Together with the fraction, C ８ C fractions such as styrene １０ The fractions methylindene, 1,3-dimethylstyrene, etc., as well as naphthalene, vinylnaphthalene, vinylanthracene, p-tert-butylstyrene, etc. are also used as raw materials, and these C ８ ~C １０ The fractions and the like can be copolymerized as a mixture with, for example, a Friedel-Crafts catalyst to obtain the copolymer. ９ The petroleum resin may be a modified petroleum resin modified with a compound having a hydroxyl group, an unsaturated carboxylic acid compound, or the like.

[0187] Dicyclopentadiene resin is a petroleum resin produced using dicyclopentadiene, which is obtained by dimerizing cyclopentadiene, as the main raw material.

[0188] Temper phenol resins can be obtained, for example, by reacting a temper with various phenols using a Friedel-Crafts catalyst, or by further condensing the mixture with formalin.

[0189] Terpene resins are solid resins obtained by blending turpentine oil, which is obtained simultaneously when rosin is obtained from pine trees, or a polymerizable component separated from the turpentine oil, and polymerizing the blend using a Friedel-Crafts catalyst. Examples of terpene resins include β-pinene resin and α-pinene resin.

[0190] Rosin resin is the residue remaining after collecting balsams such as pine resin (pine tar), which is the sap of plants in the Pinaceae family, and distilling turpentine essential oil. It includes natural resins whose main component is rosin acid (apietic acid, palustric acid, isopimaric acid, etc.), as well as modified and hydrogenated resins obtained by modifying, hydrogenating, or otherwise processing these. Examples include natural resin rosin, its polymerized rosin, and partially hydrogenated rosin; glycerin ester rosin, its partially hydrogenated rosin, fully hydrogenated rosin, and polymerized rosin; pentaerythritol ester rosin, its partially hydrogenated rosin, and polymerized rosin. Natural resin rosins include gum rosin, tall oil rosin, and wood rosin, which are contained in raw pine tar and tall oil.

[0191] The alkylphenol resin can be obtained, for example, by a condensation reaction between an alkylphenol and formaldehyde in the presence of a catalyst.

[0192] These resins may be used alone or in combination of two or more.

[0193] The blending amount of the resin is not particularly limited, but is preferably 5 to 40 parts by mass per 100 parts by mass of the rubber component.

[0194] As the vulcanization accelerator, those commonly used in the tire industry can be used, such as guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, and dithiocarbamate compounds.

[0195] Examples of guanidine compounds include 1,3-diphenylguanidine, 1,3-o-toluylguanidine, 1-o-toluylbiguanide, and di-o-toluylguanidine salts of dicatechol borate.

[0196] Examples of sulfenamide compounds include N-(tert-butyl)-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazolyl sulfenamide, and the like.

[0197] Examples of thiazole compounds include 2-mercaptobenzothiazole (MBT), di-2-benzothiazolyl disulfide (MBTS), 2-(4'-morpholinodithio)benzothiazole (MDB), zinc mercaptobenzothiazole (ZnMBT), and 2-mercaptobenzothiazole cyclohexylamine salt (CMBT).

[0198] Examples of thiuram compounds include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram tetrasulfide (DPTT), tetramethylthiuram monosulfide (TMTM), tetrabutylthiuram disulfide (TBTD), and tetrakis(2-ethylhexyl)thiuram disulfide.

[0199] Examples of dithiocarbamate compounds include zinc dimethyldithiocarbamate (ZnMDC), zinc diethyldithiocarbamate (ZnEDC), zinc ethylphenyldithiocarbamate (ZnEPDC), zinc dibutyldithiocarbamate (ZnBDC), zinc N-pentamethylenedithiocarbamate (ZnPDC), piperidine pentamethylenedithiocarbamate (PPDC), zinc dibenzyldithiocarbamate, sodium dibutyldithiocarbamate, copper dimethyldithiocarbamate (CuMDC), ferric dimethyldithiocarbamate (FeMDC), and tellurium diethyldithiocarbamate (TeEDC).

[0200] These vulcanization accelerators may be used alone or in combination of two or more.

[0201] The amount of the vulcanization accelerator to be added is not particularly limited, but is preferably 1 to 10 parts by mass per 100 parts by mass of the rubber component.

[0202] Examples of the vulcanizing agent include sulfur, peroxides, quinonedioxime compounds, nitrosobenzene compounds, thio compounds, and dismaleimide compounds, with sulfur being preferred.

[0203] Examples of sulfur include oil-treated sulfur obtained by adding 2 to 10 mass % of oil commonly used in the rubber industry, such as naphthenic oil, to sulfur, soluble sulfur (powdered sulfur), sulfur flowers, highly dispersible sulfur, insoluble sulfur, precipitated sulfur, surface-treated sulfur, colloidal sulfur, sulfur chloride, sulfur monochloride, sulfur dichloride, etc. The amount of sulfur to be added is not particularly limited, but is preferably 0.01 to 10 parts by mass per 100 parts by mass of the rubber component.

[0204] Examples of the peroxide include dicumyl peroxide and 2,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane.

[0205] Examples of the quinonedioxime compound include p-quinonedioxime and o,o'-dibenzoyl-p-quinonedioxime.

[0206] The nitrobenzene compound includes poly-p-dinitrosobenzene.

[0207] The thio compound includes 4,4'-dithiomorpholine.

[0208] Examples of the bismaleimide compound include N,N'-m-phenylenebismaleimide and N,N'-m-phenylenebiscitraconimide.

[0209] Examples of the crosslinking agent include a sulfur crosslinking agent, a sulfur compound crosslinking agent, a quinoid crosslinking agent, and a maleimide crosslinking agent.

[0210] Examples of sulfur crosslinking agents include powdered sulfur, sulfur flowers, highly dispersible sulfur, insoluble sulfur, precipitated sulfur, surface-treated sulfur, colloidal sulfur, sulfur chloride, sulfur monochloride, sulfur dichloride, etc. These sulfur crosslinking agents may be used alone or in combination of two or more.

[0211] When a sulfur crosslinking agent is used, a crosslinking accelerator can also be used in combination.

[0212] Examples of the crosslinking accelerator include aldehyde ammonias such as hexamethylenetetramine and acetaldehyde ammonia; aldehyde amines such as n-butylaldehyde-aniline condensation products, butylaldehyde-monobutylamine condensation products, heptaldehyde-aniline reaction products, and tricrotonylidene tetramine; guanidine salts such as diphenylguanidine, di-o-tolylguanidine, 1-(o-tolyl)biguanide, and di-ortho-tolyl guanidine salt of dicatechol boric acid; imidazolines such as 2-mercaptoimidazoline; 2-mercaptobenzothiazole, 2-mercaptothiazoline, dibenzothiazyl disulfide, zinc salt of 2-mercaptobenzothiazole, sodium salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, and 2-(2,4-diphenyl guanidine). Thiazoles such as N-cyclohexyl-2-benzothiazyl sulfenamide, N,N-dicyclohexyl-2-benzothiazyl sulfenamide, N-oxydiethylene-2-benzothiazyl sulfenamide, N,N-diisopropyl-2-benzothiazyl sulfenamide, N-tert-butyl-2-benzothiazyl sulfenamide, etc.; thioureas such as thiocarbanide, ethylene thiourea (2-mercaptoimidazoline), diethyl thiourea, dibutyl thiourea, mixed alkyl thiourea, trimethyl thiourea, dilauryl thiourea, etc.;Sodium dimethyl dithiocarbamate, sodium diethyl dithiocarbamate, sodium di-n-butyl carbamate, lead dimethyl dithiocarbamate, lead diamyl dithiocarbamate, zinc dimethyldithiocarbamate, zinc diamyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate, zinc dipendyl dithiocarbamate, zinc N-pentamethylene dithiocarbamate, zinc ethylphenyl dithiocarbamate, selenium dimethyl dithiocarbamate, selenium diethyl dithiocarbamate, tellurium diethyl dithiocarbamate, cadmium diethyl dithiocarbamate, copper dimethyl dithiocarbamate, iron dimethyl dithiocarbamate, bismuth dimethyl dithiocarbamate, piperidine dimethyl dithiocarbamate, methylpentamethylene dithiocarbamate dithiocarbamates such as pipecoline dithioate and activated dithiocarbamates; thiurams such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, activated tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N,N'-dimethyl-N,N'-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, and mixed alkyl thiuram disulfides; xanthates such as sodium isopropyl xanthate, zinc isopropyl xanthate, and zinc butyl xanthate; 4,4'-dithiodimorpholine, aminodialkyldithiophosphate, zinc-o,o-n-butyl phosphorodithioate, 3-mercaptoimidazoline-thione-2, and thioglycolic acid esters. These crosslinking accelerators may be used alone or in combination of two or more.

[0213] Examples of sulfur compound crosslinking agents include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram, tetrasulfide, dimorpholyl disulfide, 2-(4'-morpholinodithio)benzothiazole, etc. These sulfur compound crosslinking agents may be used alone or in combination of two or more.

[0214] Examples of crosslinking accelerators used to improve the crosslinking rate of such sulfur compound crosslinking agents include N-(tert-butyl)-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazyl sulfenamide, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, cyclohexylamine salt of 2-mercaptobenzothiazole, and thiourea accelerators. These may be used alone or in combination of two or more.

[0215] Examples of quinoid crosslinking agents include p-quinone dioxime, O,O'-dipentoyl-p-quinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, etc. These quinoid crosslinking agents can be used alone or in combination of two or more.

[0216] Examples of maleimide crosslinking agents include N,N'-1,3-phenylene bismaleimide (also known as N,N'-m-phenylene bismaleimide), 1,3-bis(citraconimidomethyl)benzene, N,N'-1,2-phenylene bismaleimide, N,N'-1,4-phenylene bismaleimide, N,N'-(4,4'-diphenylmethane)bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl]methane, etc. These maleimide crosslinking agents can be used alone or in combination of two or more.

[0217] The amount of the crosslinking agent to be added is not particularly limited, but is preferably 0.01 to 10 parts by mass per 100 parts by mass of the rubber component.

[0218] When the rubber composition (vulcanized rubber) containing the triarylamine compound of the present invention is applied to tire components such as treads and sidewalls, it can be processed well, and the produced rubber products exhibit good weather resistance.

[0219] [4] Vulcanized Rubber The present invention encompasses a vulcanized rubber containing a rubber component and the triarylamine compound of the present invention.

[0220] The vulcanized rubber of the present invention is obtained by vulcanizing a rubber composition before vulcanization (hereinafter referred to as "unvulcanized rubber composition") that contains a rubber component and the triarylamine compound of the present invention.

[0221] The unvulcanized rubber composition is as described above in [3] Rubber composition.

[0222] The vulcanized rubber contains, per 100 parts by mass of the rubber component, preferably 0.2 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 8 parts by mass, even more preferably 0.7 parts by mass to 7 parts by mass, and particularly preferably 1 part by mass to 5 parts by mass of the triarylamine compound of the present invention.

[0223] The vulcanized rubber more preferably contains, as the rubber component, at least one rubber component selected from the group consisting of NR, IR, SBR, EPDM, and BR, even more preferably contains at least one rubber component selected from the group consisting of NR, IR, SBR, and BR, and particularly preferably contains at least one rubber component selected from the group consisting of NR and IR.

[0224] The triarylamine compound of the present invention has a specific structure, and in vulcanized rubber, compared with conventional triarylamine compounds (Patent Document 2), it maintains weather resistance to the same degree and has better processability.

[0225] The triarylamine compound of the present invention is believed to quickly trap and detoxify radicals generated in rubber, and also to react with oxidizing substances such as ozone before the rubber component reacts with them.

[0226] [5] Rubber Products The present invention encompasses rubber products in which a rubber composition (or vulcanized rubber) containing a rubber component and the triarylamine compound represented by formula (1) of the present invention is applied to tires, rubber crawlers, or seismic isolation rubber. The rubber products of the present invention contain the rubber composition containing the triarylamine compound of the present invention, can be well processed, and the manufactured rubber products exhibit good weather resistance.

[0227] The rubber crawler comprises steel cords, an intermediate rubber layer covering the steel cords, a core bar disposed on the intermediate rubber layer, and a main rubber layer surrounding the intermediate rubber layer and the core bar, and further has a plurality of lugs on the contact surface side of the main rubber layer. The rubber composition of the present invention may be used in any part of the rubber crawler. Because the rubber composition of the present invention has excellent crack growth resistance, it is preferably used in the main rubber layer, particularly the lugs.

[0228] Seismic isolation rubber The seismic isolation rubber comprises a laminate in which soft layers and hard layers are alternately laminated, and a plug that is press-fitted into a hollow portion formed in the center of the laminate. The rubber composition of the present invention can be used for either or both of the soft layer and the plug.

[0229] In a tire, the application portion of the rubber composition (or vulcanized rubber) of the present invention is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include the tread, base tread, sidewall, side reinforcing rubber, and bead filler.

[0230] The present invention encompasses a tire in which a rubber composition (or vulcanized rubber) containing a rubber component, i.e., a triarylamine compound represented by formula (1) of the present invention, is applied to tire components. When the rubber composition (or vulcanized rubber) containing the triarylamine compound of the present invention is applied to tire components such as a tread and sidewall, it can be processed well, and the tire produced exhibits good weather resistance.

[0231] A tire is manufactured using the rubber composition (or vulcanized rubber) of the present invention. Tire components are manufactured by mixing or kneading the rubber composition of the present invention using a Banbury mixer, roll, intensive mixer, kneader, single-screw extruder, twin-screw extruder, or the like. Subsequently, in an extrusion step, the rubber composition is extruded and processed, and molded into, for example, tread components or sidewall components.

[0232] Next, the rubber composition is applied and molded into a green tire using a conventional method on a tire building machine. The green tire is then heated and pressurized in a vulcanizer to obtain a tire. Components typically used in tire manufacturing, such as a carcass layer, belt layer, and tread layer, each composed of an unvulcanized rubber composition and / or cords, are sequentially applied onto a tire building drum, and the drum is removed to obtain a green tire. The green tire is then heated and vulcanized (vulcanized rubber) using conventional methods to produce a desired tire (e.g., a pneumatic tire).

[0233] The tire is preferably a pneumatic tire (radial tire, bias tire, etc.), a solid tire, etc. The tire is preferably used as a passenger car tire, a heavy-duty tire, a motorcycle tire, a studless tire, a large tire for trucks, buses, etc. The tire is more preferably used as a passenger car tire.

[0234] The shape, structure, size and material of the tire are not particularly limited and may be appropriately selected depending on the purpose.

[0235] The tire components are preferably a tread portion, a sidewall portion, a bead area portion, a belt portion, a carcass portion, a shoulder portion, etc., and more preferably tire components such as a tire tread portion, a sidewall portion, etc.

[0236] The tread portion has a tread pattern and is the outer shell of the tire that directly contacts the road surface, protecting the carcass and preventing wear and damage. Within the tread portion, it refers to the cap tread that constitutes the tire's ground contact area and / or the base tread disposed inside the cap tread.

[0237] The sidewall portion is a portion of a pneumatic radial tire extending from the lower side of the shoulder portion to the bead portion, and protects the carcass and is the portion that is most subject to bending during running.

[0238] The bead area is the part that secures both ends of the carcass cord and also secures the tire to the rim. The bead is made of bundled high-carbon steel.

[0239] The belt is a reinforcing band stretched circumferentially between the radial tread and carcass. It tightens the carcass like a barrel hoop, increasing the rigidity of the tread.

[0240] The carcass is a cord layer portion that forms the skeleton of the tire, and serves to withstand the load, impact, and inflation pressure that the tire receives.

[0241] The shoulder portion is the shoulder part of the tire and serves to protect the carcass.

[0242] The tires are manufactured according to conventional methods in the field of tires. The gas used to fill the tires is normal or oxygen-adjusted air, or an inert gas such as nitrogen, argon, or helium.

[0243] When a rubber composition (or vulcanized rubber) containing the triarylamine compound of the present invention is applied to tire components such as a tread or sidewall, it can be processed well, and the produced tire exhibits good weather resistance.

[0244] Other Applications The rubber composition (or vulcanized rubber) of the present invention can be preferably used for various rubber members such as vibration-proof rubber, conveyor belts, and hoses.

[0245] [6] Method for preventing aging of vulcanized rubber The present invention includes a method for preventing aging of vulcanized rubber by applying the triarylamine compound represented by formula (1) of the present invention to vulcanized rubber.

[0246] When a rubber composition (vulcanized rubber) containing the triarylamine compound of the present invention is applied to rubber products such as tires, rubber crawlers, and seismic isolation rubber, or tire components such as treads and sidewalls, it can be processed well, and the manufactured rubber products such as tires, rubber crawlers, and seismic isolation rubber exhibit good weather resistance.

[0247] [7] Method for producing rubber composition The present invention includes a method for producing the rubber composition of the present invention.

[0248] <Method for producing rubber composition> A method comprising: (1) a step of kneading components such as a rubber component, the triarylamine compound represented by formula (1) of the present invention, carbon black and / or an inorganic filler; and (2) a step of mixing a vulcanizing agent (sulfur, etc.) and, if necessary, other components, with the unvulcanized rubber composition obtained in the step (1), followed by kneading.

[0249] Step (1) In step (1), the rubber component, the triarylamine compound of the present invention represented by formula (1), carbon black and / or an inorganic filler, and other components are kneaded.

[0250] In step (1), the blending amount of the triarylamine compound represented by formula (1) of the present invention is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 1 to 8 parts by mass, per 100 parts by mass of the rubber component.

[0251] The mixing temperature in step (1) is preferably 60° C. to 190° C., more preferably 70° C. to 160° C., and even more preferably 80° C. to 150° C. By adjusting the mixing temperature to 60° C. to 190° C., the reaction proceeds smoothly and rubber degradation can be suppressed.

[0252] The kneading time in step (1) is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 60 seconds to 7 minutes. By adjusting the mixing time to 10 seconds to 20 minutes, the reaction proceeds smoothly and productivity can be improved.

[0253] When proceeding from step (1) to step (2), the mixture is preferably cured so that the maximum temperature of the mixture is 60°C or less.

[0254] In the kneading method, the kneading operation may be repeated to uniformly disperse each component.

[0255] Step (2) In step (2), a vulcanizing agent (such as sulfur) and other components, if necessary, are added to the mixture (unvulcanized rubber composition) obtained in step (1), and mixed to produce an unvulcanized rubber composition. Step (2) is the final stage of kneading.

[0256] Step (2) is preferably carried out under heating conditions, and the heating temperature is preferably 60°C to 120°C, more preferably 65°C to 100°C.

[0257] The mixing (or kneading) time in step (2) is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 60 seconds to 5 minutes.

[0258] When proceeding from step (2) to the vulcanization step, the mixture is preferably cured so that the maximum temperature of the mixture is 70°C or less.

[0259] <Vulcanization step> After mixing a vulcanizing agent (sulfur, etc.) with a rubber composition (unvulcanized rubber composition), the mixture is vulcanized by heating (150°C x 25 minutes) using a vulcanization press to obtain vulcanized rubber.

[0260] In the method for producing the rubber composition of the present invention, various compounding agents such as antioxidants, waxes, stearic acid, zinc oxide, vulcanization accelerators, etc. may be added in each step as needed. The other compounding agents may be added in any one of the steps, or may be added separately in each step.

[0261] When a rubber composition (or vulcanized rubber) containing the triarylamine compound of the present invention is applied to tire components such as a tread or sidewall, it can be processed well, and the produced tire exhibits good weather resistance.

[0262] The present invention will be specifically described below by showing Production Examples and Examples, which are merely illustrative and are not intended to limit the scope of the present invention.

[0263] [1] Production of the Triarylamine Compound of the Present Invention [1-1] Production of Triarylamine Compound A <Step 1> 38.0 g of cesium fluoride was added to a solution of 12.3 g of p-anisidine and 4-fluoronitrobenzene in 200 mL of DMSO, and the mixture was reacted for 24 hours at 120° C. After cooling the reaction solution, 400 mL of water was added to terminate the reaction, and the precipitated solid was filtered, washed with methanol, and dried to obtain Intermediate 1 (36.5 g, yield 99%).

[0264] 1 H-NMR (500MHz, DMSO-d6, δppm): 8.12-8.15 (4H, m), 7.10-7.14 (6H, m), 6.95-6.98 (2H, m), 3.85 (3H, s)

[0265] <Step 2> Intermediate 1 (36.9 g) was suspended in 500 mL of ethanol, and then 227.6 g of tin(II) chloride dihydrate was added. The mixture was refluxed for 24 hours. The reaction mixture was concentrated, and 500 mL of water was added to dissolve the precipitated solid. The pH was adjusted to 8 with 48% aqueous sodium hydroxide. The precipitated solid was filtered and washed with methylene chloride, and the filtrate was extracted with methylene chloride. After distilling off the solvent, the precipitated solid was dried to obtain intermediate 2 (26.6 g, 86% yield).

[0266] 1 H-NMR (500MHz, DMSO-d6, δppm): 6.91-6.93 (2H, m), 6.85-6.87 (4H, m), 6.73-6.76 (2H, m), 6.57-6.60 (4H, m), 3.76 (3H, s), 3.49 (4H, br-s)

[0267] ​​<Step 3> Intermediate 2 (13.0 g) was suspended in 100 mL of methanol, and then 12.8 g of methyl isobutyl ketone, 25.9 g of acetic acid, and 8.03 g of sodium cyanoborohydride were added, followed by a 24-hour reaction. After distilling off the solvent, 50 mL of water was added to the reaction mixture to terminate the reaction, followed by extraction with ethyl acetate. After distilling off the solvent, the residue was purified by silica gel chromatography and dried to obtain the target product (triarylamine compound A) (11.0 g, 55% yield).

[0268] 1 H-NMR (500MHz, DMSO-d6, δppm): 6.73-6.89 (8H, m), 6.47-6.49 (4H, m), 3.76 (3H, s), 3.40-3.50 (2H, m), 3.10-3.30 (2H, m), 1.72-1.78 (2H, m), 1.43-1.49 (2H, m), 1.15-1.27 (8H, m), 0.90-0.94 (12H, m)

[0269] (Triarylamine Compound A, Me: CH3-) N4-(1,3-dimethylbutyl)-N1-[4-(1,3-dimethylbutylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine

[0270] [1-2] Production of Triarylamine Compound B <Step 1> 38.0 g of cesium fluoride was added to a solution of 12.3 g of p-anisidine and 4-fluoronitrobenzene in 200 mL of DMSO, and the mixture was reacted for 24 hours at 120° C. After cooling the reaction solution, 400 mL of water was added to stop the reaction, and the precipitated solid was filtered, washed with methanol, and dried to obtain Intermediate 1 (36.5 g, yield 99%).

[0271] 1 H-NMR (500MHz, DMSO-d6, δppm): 8.12-8.15 (4H, m), 7.10-7.14 (6H, m), 6.95-6.98 (2H, m), 3.85 (3H, s)

[0272] ​​<Step 2> Intermediate 1 (36.9 g) was suspended in 500 mL of ethanol, and then 227.6 g of tin(II) chloride dihydrate was added. The mixture was refluxed for 24 hours. The reaction mixture was concentrated, and 500 mL of water was added to dissolve the precipitated solid. The pH was adjusted to 8 with 48% aqueous sodium hydroxide. The precipitated solid was filtered and washed with methylene chloride, and the filtrate was extracted with methylene chloride. After distilling off the solvent, the precipitated solid was dried to obtain intermediate 2 (26.6 g, 86% yield).

[0273] 1 H-NMR (500MHz, DMSO-d6, δppm): 6.91-6.93 (2H, m), 6.85-6.87 (4H, m), 6.73-6.76 (2H, m), 6.57-6.60 (4H, m), 3.76 (3H, s), 3.49 (4H, br-s)

[0274] <Step 3> Intermediate 2 (13.0 g) was suspended in 100 mL of methanol, and then 8.1 g of 3-pentanone, 25.9 g of acetic acid, and 7.5 g of sodium cyanoborohydride were added, followed by a 24-hour reaction. After distilling off the solvent, 50 mL of water was added to the reaction mixture to terminate the reaction, followed by extraction with ethyl acetate. After distilling off the solvent, the residue was purified by silica gel chromatography and dried to obtain the target product (triarylamine compound B) (11.4 g, 60% yield).

[0275] 1 H-NMR (500MHz, CDCl3, δppm): 6.86-6.90 (6H, m), 6.70-6.74 (2H, m), 6.45-6.49 (4H, m), 3.76 (3H, s), 3.24-3.28 (2H, m), 3.13-3.17 (2H, m), 1.42-1.78 (8H, m), 0.92 (12H, t)

[0276] (Triarylamine Compound B, Me: CH3-) N1-(1-ethylpropyl)-N4-[4-(1-ethylpropylamino)phenyl]-N4-(4-methoxyphenyl)benzene-1,4-diamine

[0277] ​​[1-3] Production of Triarylamine Compound C <Step 1> 38.0 g of cesium fluoride was added to a solution of 12.3 g of p-anisidine and 4-fluoronitrobenzene in 200 mL of DMSO, and the mixture was reacted for 24 hours at 120° C. After cooling the reaction solution, 400 mL of water was added to stop the reaction, and the precipitated solid was filtered, washed with methanol, and dried to obtain Intermediate 1 (36.5 g, yield 99%).

[0278] 1 H-NMR (500MHz, DMSO-d6, δppm): 8.12-8.15 (4H, m), 7.10-7.14 (6H, m), 6.95-6.98 (2H, m), 3.85 (3H, s)

[0279] <Step 2> Intermediate 1 (36.9 g) was suspended in 500 mL of ethanol, and then 227.6 g of tin(II) chloride dihydrate was added. The mixture was refluxed for 24 hours. The reaction mixture was concentrated, and 500 mL of water was added to dissolve the precipitated solid. The pH was adjusted to 8 with 48% aqueous sodium hydroxide. The precipitated solid was filtered and washed with methylene chloride, and the filtrate was extracted with methylene chloride. After distilling off the solvent, the precipitated solid was dried to obtain intermediate 2 (26.6 g, 86% yield).

[0280] 1 H-NMR (500MHz, DMSO-d6, δppm): 6.91-6.93 (2H, m), 6.85-6.87 (4H, m), 6.73-6.76 (2H, m), 6.57-6.60 (4H, m), 3.76 (3H, s), 3.49 (4H, br-s)

[0281] <Step 3> Intermediate 2 (12.0 g) was suspended in 100 mL of methanol, and then 11.1 g of 2-octanone, 25.9 g of acetic acid, and 6.9 g of sodium cyanoborohydride were added, followed by a 24-hour reaction. After distilling off the solvent, 50 mL of water was added to the reaction mixture to terminate the reaction, followed by extraction with ethyl acetate. After distilling off the solvent, the residue was purified by silica gel chromatography and dried to obtain the target product (triarylamine compound C) (13.1 g, 60% yield).

[0282] 1 ​​​H-NMR (500MHz, CDCl3, δppm): 6.86-6.90 (6H, m), 6.70-6.74 (2H, m), 6.45-6.49 (4H, m), 3.76 (3H, s), 3.24-3.28 (2H, m), 3.13-3.17 (2H, m), 1.20-1.48 (20H, m), 1.15 (6H, d), 0.88 (6H, t)

[0283] (Triarylamine Compound C, Me: CH3-) N1-(4-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine

[0284] [1-4] Production of Triarylamine Compound D <Step 1> 38.0 g of cesium fluoride was added to a solution of 12.3 g of p-anisidine and 28.5 g of 4-fluoronitrobenzene in 200 mL of DMSO, and the mixture was reacted for 24 hours at 120° C. After cooling the reaction solution, 400 mL of water was added to stop the reaction, and the precipitated solid was filtered, washed with methanol, and dried to obtain Intermediate 1 (36.5 g, yield 99%).

[0285] 1 H-NMR (500MHz, DMSO-d6, δppm): 3.85 (3H, s), 6.95-6.98 (2H, m), 7.10-7.14 (6H, m), 8.12-8.15 (4H, m)

[0286] <Step 2> Intermediate 1 (36.5 g) was suspended in 333 mL of methanol and 167 mL of DMF, and then 3.7 g of palladium carbon was added. Hydrogen gas was then sealed in and the mixture was allowed to react for 24 hours. The reaction solution was filtered to remove the palladium carbon, and then 400 mL of water was added. The precipitated solid was filtered, washed with methanol, and dried to obtain intermediate 2 (30.5 g, 99% yield).

[0287] 1 ​​H-NMR (500MHz, DMSO-d6, δppm): 3.49 (4H, br-s), 3.76 (3H, s), 6.57-6.60 (4H, m), 6.73-6.76 (2H, m), 6.85-6.87 (4H, m), 6.91-6.93 (2H, m)

[0288] <Step 3> Intermediate 2 (30.5 g) was suspended in 300 mL of methanol, and then 18.7 g of 2-butanone, 25.9 g of acetic acid, and 16.3 g of sodium cyanoborohydride were added, followed by a 24-hour reaction. After distilling off the solvent, 150 mL of water was added to the reaction mixture to terminate the reaction, followed by extraction with ethyl acetate. After distilling off the solvent, the residue was purified by silica gel chromatography and dried to obtain the target product (triarylamine compound D) (33.4 g, 80% yield).

[0289] 1 H-NMR (400MHz, CDCl3, δppm): 0.94 (6H, t), 1.15 (6H, d), 1.38-1.50 (2H, m), 1.53-1.65 (2H, m), 3.31 (4H, brs), 3.74 (3H, s), 6.47 (4H, d), 6.72 (2H, d), 6.86-6.92 (6H, m)

[0290] (Triarylamine Compound D, Me: CH3-) N1-(4-methoxyphenyl)-N4-(1-methylpropyl)-N1-[4-(1-methylpropylamino)phenyl]benzene-1,4-diamine

[0291] [1-5] Production of Triarylamine Compound E <Step 1> 38.0 g of cesium fluoride was added to a solution of 12.3 g of p-anisidine and 28.5 g of 4-fluoronitrobenzene in 200 mL of DMSO, and the mixture was reacted for 24 hours at 120° C. After cooling the reaction solution, 400 mL of water was added to stop the reaction, and the precipitated solid was filtered, washed with methanol, and dried to obtain Intermediate 1 (36.5 g, yield 99%).

[0292] 1 ​​H-NMR (500MHz, DMSO-d6, δppm): 3.85 (3H, s), 6.95-6.98 (2H, m), 7.10-7.14 (6H, m), 8.12-8.15 (4H, m)

[0293] <Step 2> Intermediate 1 (36.5 g) was suspended in 333 mL of methanol and 167 mL of DMF, and then 3.7 g of palladium carbon was added. Hydrogen gas was then sealed in and the mixture was allowed to react for 24 hours. The reaction solution was filtered to remove the palladium carbon, and then 400 mL of water was added. The precipitated solid was filtered, washed with methanol, and dried to obtain intermediate 2 (30.5 g, 99% yield).

[0294] 1 H-NMR (500MHz, DMSO-d6, δppm): 3.49 (4H, br-s), 3.76 (3H, s), 6.57-6.60 (4H, m), 6.73-6.76 (2H, m), 6.85-6.87 (4H, m), 6.91-6.93 (2H, m)

[0295] <Step 3> Intermediate 2 (30.5 g) was suspended in 300 mL of methanol, and then 30.0 g of 4-heptanone, 25.9 g of acetic acid, and 16.3 g of sodium cyanoborohydride were added, followed by a 24-hour reaction. After distilling off the solvent, 150 mL of water was added to the reaction mixture to terminate the reaction, followed by extraction with ethyl acetate. After distilling off the solvent, the residue was purified by silica gel chromatography and dried to obtain the target product (triarylamine compound E) (40.1 g, 90% yield).

[0296] 1 H-NMR (400MHz, CDCl3, δppm): 0.91 (12H, t), 1.28-1.56 (16H, m), 3.15-3.32 (4H, m), 3.75 (3H, s), 6.45 (4H, d), 6.73 (2H, d), 6.84-7.94 (6H, m)

[0297] (Triarylamine Compound E, Me: CH3-) N1-(4-methoxyphenyl)-N4-(1-propylbutyl)-N1-[4-(1-propylbutylamino)phenyl]benzene-1,4-diamine ​​

[0298] [1-6] Production of Triarylamine Compound F <Step 1> 38.0 g of cesium fluoride was added to a solution of 12.3 g of p-anisidine and 28.5 g of 4-fluoronitrobenzene in 200 mL of DMSO, and the mixture was reacted for 24 hours at 120° C. After cooling the reaction solution, 400 mL of water was added to stop the reaction, and the precipitated solid was filtered, washed with methanol, and dried to obtain Intermediate 1 (36.5 g, yield 99%).

[0299] 1 H-NMR (500MHz, DMSO-d6, δppm): 3.85 (3H, s), 6.95-6.98 (2H, m), 7.10-7.14 (6H, m), 8.12-8.15 (4H, m)

[0300] <Step 2> Intermediate 1 (36.5 g) was suspended in 333 mL of methanol and 167 mL of DMF, and then 3.7 g of palladium carbon was added. Hydrogen gas was then sealed in and the mixture was allowed to react for 24 hours. The reaction solution was filtered to remove the palladium carbon, and then 400 mL of water was added. The precipitated solid was filtered, washed with methanol, and dried to obtain intermediate 2 (30.5 g, 99% yield).

[0301] 1 H-NMR (500MHz, DMSO-d6, δppm): 3.49 (4H, br-s), 3.76 (3H, s), 6.57-6.60 (4H, m), 6.73-6.76 (2H, m), 6.85-6.87 (4H, m), 6.91-6.93 (2H, m)

[0302] <Step 3> Intermediate 2 (30.5 g) was suspended in 300 mL of methanol, and then 15.0 g of acetone, 13.3 g of acetic acid, and 16.3 g of sodium cyanoborohydride were added, followed by a 24-hour reaction. After distilling off the solvent, 150 mL of water was added to the reaction mixture to terminate the reaction, followed by extraction with ethyl acetate. After distilling off the solvent, the residue was purified by silica gel chromatography and dried to obtain the target product (triarylamine compound F) (35.0 g, 90% yield).

[0303] 1 ​​​H-NMR (400MHz, CDCl3, δppm): 1.19 (12H, d), 3.10-3.38 (2H, m), 3.40-3.62 (2H, m), 3.75 (3H, s), 6.40-6.58 (4H, m), 6.68-6.77 (2H, m), 6.79-7.20 (6H, m)

[0304] (Triarylamine Compound F, Me: CH3-) N1-(4-methoxyphenyl)-N4-(1-isopropyl)-N1-[4-(1-isopropylamino)phenyl]benzene-1,4-diamine

[0305] [2] Rubber composition manufacturing process (1) (unvulcanized rubber) As shown in Table 1, a rubber component, a triarylamine compound, carbon black, silica, a silane coupling agent, a wax, an antioxidant, etc. were blended in their respective proportions (parts by mass) and mixed to obtain a mixture.

[0306] Mixing temperature: 140℃ Mixing time: 4 minutes

[0307] Next, this mixture was kneaded in a Banbury mixer and cured until the temperature of the mixture reached 60°C or less to produce an unvulcanized rubber composition.

[0308] Step (2) (Unvulcanized Rubber) To the unvulcanized rubber composition obtained in step (1), vulcanizing agents (sulfur) and the like were added as shown in Table 1, and the mixture was kneaded while adjusting the maximum temperature of the mixture to 70°C or less.

[0309] The proportions (parts by mass) of "other chemicals" shown in Table 1 are the sum of the proportions (parts by mass) mixed in step (1) and step (2).

[0310] Step (3) Vulcanization Step The unvulcanized rubber composition obtained in step (2) was vulcanized by heating at 150°C for 25 minutes using a vulcanization press to obtain a vulcanized rubber.

[0311] The rubber compositions produced according to the compounding recipes shown in Table 1 were evaluated for ozone resistance and processability.

[0312] [3] Performance test of vulcanized rubber (1) Weather resistance (ozone resistance) test In accordance with JIS K 6259-1, a dynamic ozone degradation test (a test in which repeated strain is applied) was conducted to evaluate ozone resistance. The evaluation was conducted by ranking the number of cracks and classifying them according to the following criteria (A to C). The evaluation was also conducted by ranking the size and depth of the cracks and classifying them according to the following criteria (1 to 5).

[0313] (Ranking by number of cracks) A: There are a few cracks in the vulcanized rubber. B: There are a large number of cracks in the vulcanized rubber. C: There are countless cracks in the vulcanized rubber.

[0314] (Ranking by size and depth of cracks) 1: Cracks in vulcanized rubber are not visible to the naked eye, but can be seen with a 10x magnifying glass. 2: Cracks in vulcanized rubber are visible to the naked eye. 3: Cracks in vulcanized rubber are deep and relatively large (less than 1mm). 4: Cracks in vulcanized rubber are deep and large (1mm or more but less than 3mm). 5: Cracks in vulcanized rubber are 3mm or more, or the vulcanized rubber may break.

[0315] (2) Test of processability (viscosity) Using an unvulcanized viscoelasticity device RPA2000 (manufactured by ALPHA TECHNOLOGIES), the dynamic storage (shear) modulus of elasticity G' was measured under conditions of a temperature of 130°C, a strain (torsion angle) of 1°, and a frequency of 100 cpm.

[0316] The evaluation results were indexed by setting the value of Comparative Example 1 to 100 and the values ​​of Examples 1 and 3. The evaluation results were indexed by setting the value of Comparative Example 2 to 100 and the values ​​of Examples 2 and 4. The smaller the index value, the lower the viscosity of the unvulcanized rubber and the better the processability.

[0317]

[0318] NR: Natural rubber BR: Butadiene rubber, cis-1,4 bond content = 96% by mass or more SBR-1: Styrene-butadiene rubber, oil-extended, manufactured by ENEOS Materials Corporation, bound styrene content = 45% by mass, vinyl bond content in butadiene moiety = 19% by mass, glass transition temperature = -30°C, contains 25 parts by mass of oil-extended component SBR-2: Styrene-butadiene rubber, manufactured by ENEOS Materials Corporation, bound styrene content = 35% by mass, vinyl bond content in butadiene moiety = 26% by mass, glass transition temperature = -60°C Carbon black-1: Manufactured by Asahi Carbon Co., Ltd., trade name "Asahi #65" Carbon black-2: Manufactured by Asahi Carbon Co., Ltd., trade name "Asahi #78" Silica: Manufactured by Tosoh Silica Industry Co., Ltd., trade name "Nipsil AQ" Silane coupling agent: Bis(triethoxysilylpropyl) polysulfide, manufactured by Shin-Etsu Chemical Co., Ltd., trade name "ABC-856" Wax: Microcrystalline wax, total amount of Nippon Seiro Co., Ltd.'s product name "Ozoace 0280" and Nippon Seiro Co., Ltd.'s product name "Ozoace 0701" Antioxidant TMQ, 2,2,4-trimethyl-1,2-dihydroquinoline polymer

[0319] A conventional triarylamine compound was synthesized with reference to Patent Document 2. A conventional triarylamine compound was used for the comparative example. Conventional Triarylamine Compound (Patent Document 2)

[0320] (Conventional product)

[0321] In the examples, triarylamine compounds A and C were used.

[0322] Triarylamine Compound A ([1-1] Preparation of Triarylamine Compound A)

[0323] (Triarylamine Compound A, Me: CH3-)

[0324] Triarylamine Compound C ([1-3] Preparation of Triarylamine Compound C)

[0325] (Triarylamine compound C, Me: CH3-)

[0326] [4] Performance of vulcanized rubber (1) Explanation of weather resistance (ozone resistance) The vulcanized rubbers of Examples 1 to 4 contained the triarylamine compounds (triarylamine compounds A and C) represented by formula (1) of the present invention, and their weather resistance (ozone resistance) was equally excellent compared to the vulcanized rubbers (prior art) of Comparative Examples 1 and 2. The vulcanized rubbers containing the triarylamine compounds represented by formula (1) of the present invention can be evaluated as exhibiting good weather resistance.

[0327] Triarylamine compounds B, D, E, and F also showed results equivalent to those of triarylamine compounds A and C in terms of weather resistance.

[0328] (2) Explanation of Processability The vulcanized rubbers of Examples 1 to 4 contained the triarylamine compounds (triarylamine compounds A and C) represented by formula (1) of the present invention, and were superior in processability (viscosity (INDEX)) to the vulcanized rubbers (prior art) of Comparative Examples 1 and 2. The vulcanized rubbers containing the triarylamine compounds represented by formula (1) of the present invention can be evaluated as exhibiting good processability.

[0329] Triarylamine compounds B, D, E, and F also showed results comparable to those of triarylamine compounds A and C in terms of processability.

[0330] The triarylamine compound of the present invention has a specific structure, and in vulcanized rubber, compared with conventional triarylamine compounds (Patent Document 2), it maintains weather resistance to the same degree and has better processability.

[0331] When the rubber composition (vulcanized rubber) containing the triarylamine compound of the present invention is applied to tire components such as treads and sidewalls, it can be processed well, and the produced tires exhibit good weather resistance.

Claims

1. A triarylamine compound represented by formula (1). [In formula (1), R 1 , R 2 , and R 3 and each independently represent an alkyl group having 1 to 20 carbon atoms. In formula (1), the alkyl group may have one or more substituents.] 2. The triarylamine compound according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (2). [In formula (2), R 1 represents an alkyl group having 1 to 8 carbon atoms. 4 , R 5 , R 6 , and R 7 and each independently represent an alkyl group having 1 to 8 carbon atoms. In formula (2), the alkyl group may have one or more substituents. In formula (2), R 4 and R 5 may be bonded to form a ring. 6 and R 7 may be bonded to form a ring.

3. The triarylamine compound represented by the formula (1) is N4-isopropyl-N1-[4-(isopropylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine, N4-(1,3-dimethylbutyl)-N1-[4-(1,3-dimethylbutylamino)phenyl]-N1-(4-methoxyphenyl)benzene-1,4-diamine, N1-(4-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-(4-ethoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-(3-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, 2. The triarylamine compound according to claim 1, wherein the triarylamine compound is at least one triarylamine compound selected from the group consisting of N1-(2-methoxyphenyl)-N4-(1-methylheptyl)-N1-[4-(1-methylheptylamino)phenyl]benzene-1,4-diamine, N1-(1-ethylpropyl)-N4-[4-(1-ethylpropylamino)phenyl]-N4-(4-methoxyphenyl)benzene-1,4-diamine, N1-(4-methoxyphenyl)-N4-1-methylpropyl-N1-[4-(1-methylpropylamino)phenyl]benzene-1,4-diamine, and N1-(4-methoxyphenyl)-N4-(1-propylbutyl)-N1-[4-(1-propylbutylamino)phenyl]benzene-1,4-diamine.

4. An antioxidant comprising the triarylamine compound according to any one of claims 1 to 3.

5. A rubber composition comprising a rubber component and the triarylamine compound according to any one of claims 1 to 3.

6. The rubber composition according to claim 5, comprising 0.2 to 10 parts by mass of the triarylamine compound per 100 parts by mass of the rubber component.

7. The rubber composition according to claim 5, wherein the rubber component is at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, and butadiene rubber.

8. A vulcanized rubber comprising a rubber component and the triarylamine compound according to any one of claims 1 to 3.

9. The vulcanized rubber according to claim 8, comprising 0.2 to 10 parts by mass of the triarylamine compound per 100 parts by mass of the rubber component.

10. The vulcanized rubber according to claim 8, wherein the rubber component is at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, and butadiene rubber.

11. A tire, rubber crawler, or seismic isolation rubber comprising the rubber composition according to claim 5 or the vulcanized rubber according to any one of claims 8 to 10.

12. A tire component comprising the rubber composition according to claim 5 or the vulcanized rubber according to any one of claims 8 to 10.

13. The tire component of claim 12, wherein the tire component is at least one of a tread and a sidewall.

14. A tire comprising a tire component according to claim 12 or 13.

15. A method for preventing aging of vulcanized rubber by compounding the triarylamine compound according to any one of claims 1 to 3 with the vulcanized rubber.

16. A method for producing a rubber composition, comprising: (1) a step of mixing a rubber component with the triarylamine compound according to any one of claims 1 to 3.

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