WO2008020488A1 - Compound of carboxylated disulfide amine salt, process for producing the same, rubber composition containing the compound, and pneumatic tire making use of the same in belt coating rubber and/or belt edge cushion - Google Patents

Compound of carboxylated disulfide amine salt, process for producing the same, rubber composition containing the compound, and pneumatic tire making use of the same in belt coating rubber and/or belt edge cushion Download PDF

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Publication number
WO2008020488A1
WO2008020488A1 PCT/JP2006/317590 JP2006317590W WO2008020488A1 WO 2008020488 A1 WO2008020488 A1 WO 2008020488A1 JP 2006317590 W JP2006317590 W JP 2006317590W WO 2008020488 A1 WO2008020488 A1 WO 2008020488A1
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WIPO (PCT)
Prior art keywords
rubber
compound
formula
carboxylic acid
disulfide
Prior art date
Application number
PCT/JP2006/317590
Other languages
French (fr)
Japanese (ja)
Inventor
Wonmun Choi
Yuuki Shimizu
Original Assignee
The Yokohama Rubber Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006227129A external-priority patent/JP4124794B2/en
Application filed by The Yokohama Rubber Co., Ltd. filed Critical The Yokohama Rubber Co., Ltd.
Priority to US12/377,492 priority Critical patent/US7714049B2/en
Priority to EP07792560.0A priority patent/EP2053085B1/en
Priority to CN2007800304128A priority patent/CN101506292B/en
Priority to PCT/JP2007/065927 priority patent/WO2008020604A1/en
Publication of WO2008020488A1 publication Critical patent/WO2008020488A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen

Definitions

  • Amine salt compound of carboxylic acid-containing disulfide production method thereof, rubber composition containing the same, and pneumatic tire using the same for belt coat rubber and / or belt edge cushion
  • the present invention relates to a novel carboxylic acid-containing disulfide amine salt compound.
  • the present invention relates to a disulfide ammine salt (hereinafter sometimes referred to as a disulfide ammine salt), a production method thereof, and a rubber composition containing the same.
  • the present invention also relates to a rubber composition for a tire and a pneumatic tire using the same, more specifically, a rubber composition for a tire with improved adhesion performance to a metal belt and low heat build-up, and a belt coat thereof. This relates to pneumatic tires used for rubber and z or bell edge cushions.
  • thiuram, sulfenamide, and mercaptobenzothiazole are used as rubber vulcanization accelerators.
  • Sulfenamides are slow-acting accelerators, and N—S bonds are dissociated by heat during vulcanization, and mercaptobenzothiazoles and amines are regenerated.
  • Regenerated mercaptobenzothiazol acts as a vulcanization accelerator, and amine coordinates with zinc white to promote the vulcanization reaction by activating the vulcanization system and reacting with vulcanization intermediates.
  • dibenzothiazole disulfide a disulfide-based vulcanizing agent, dissociates S — S bonds by heat and regenerates mercaptobenzothiazole. It is late and is said to be inferior to sulfenamides in terms of vulcanization acceleration ability.
  • the adhesion performance between a metal belt and rubber in a pneumatic tire is also important from the viewpoint that the tire is a composite material. If this adhesion performance is low, failure such as tire separation will occur. It will be.
  • a method has been tried to make the adhesion reaction superior by changing the blending of cobalt (C o) salt and vulcanization accelerator (Volumes 6 5 and 7 0 (1 9 9 2 (Refer to year)) There is a problem that exothermicity deteriorates. Disclosure of the invention
  • the present invention provides a carboxylic acid-containing disulfide ammine salt compound capable of improving the vulcanization speed and physical properties of the vulcanized rubber without adversely affecting the scorch time, a process for producing the same, and a rubber composition containing the same. To aim.
  • Another object of the present invention is to provide a rubber composition containing an amine salt of the carboxylic acid-containing disulfide.
  • the present invention further relates to a rubber composition improved in adhesion performance to metal bells and low heat generation suitable for use in a rubber for belt coating of a pneumatic tire and / or a belt edge cushion.
  • An object of the present invention is to provide a pneumatic tire.
  • each of R 2 and R 3 is independently hydrogen or an organic group which may have a hetero atom having 1 to 20 carbon atoms and Z or a substituent
  • X is an organic group having 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
  • a molecule represented by the formula (II) is reacted with a disulfide compound having a carboxylic acid and an amine represented by the formula (III).
  • a method for producing a carboxylic acid-containing disulfide ammine salt compound is provided.
  • each of R 2 and R 3 is independently hydrogen or an organic group which may have a hetero atom having 1 to 20 carbon atoms and Z or a substituent
  • X is an organic group having 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
  • R 2 and R 3 are independently hydrogen or an organic group optionally having 1 to 20 carbon atoms and / or a substituent, and X is 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
  • Geno rubber containing 100 parts by weight or more of natural rubber (N R) and / or polyisoprene rubber (IR) at least 30 parts by weight,
  • a rubber composition for a tire comprising 0.05 to 0.5 parts by weight of an organic metal salt as a metal content, and a pneumatic tire using the rubber composition for a belt coat rubber and a belt edge cushion.
  • an organic metal salt as a metal content
  • a pneumatic tire using the rubber composition for a belt coat rubber and a belt edge cushion is provided.
  • the amine salt of the disulfide of the above formula (I) it has a high vulcanization acceleration effect on a gen-based rubber, a halogenated butyl rubber and the like, and further adversely affects the scorch time. Therefore, the vulcanization speed and physical properties of vulcanized rubber (for example, heat aging resistance) can be improved.
  • FIG. 1 is a meridian half cross-sectional view of a typical pneumatic tire schematically showing a belt and a Z or belt edge cushion using the rubber composition according to the present invention together with other portions.
  • the amine salt compound of carboxylic acid-containing disulfide (that is, the amine salt of disulfide of the present invention) according to the present invention is a compound represented by the above formula (I).
  • R 2 and R 3 can each independently be hydrogen or an organic group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
  • a chain hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a stearyl group
  • a cyclic hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group Is mentioned.
  • the organic group chain may have a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
  • Examples of such an organic group include, for example, a methoxypropyl group, a methoxetyl group, a tetrahydrofurfuryl group, a hydroxete Examples thereof include a til group and a hydroxycyclohexyl group.
  • R, and R 2 together with the nitrogen atom to which they are attached, a heterocyclic group such as an imidazole group, a triazol group, a pyrazole group, an aziridine group, a pi-lysine group, a piperidine group, a morpholine group, A group such as a thiamorpholine group may be formed.
  • R 1 and R 2 may further have a substituent on the heterocyclic ring.
  • substituents include, for example, alkyl groups such as methyl and ethyl; halogen groups such as bromo and black mouth; hydroxyl groups, alkoxy groups, carboxyl groups, ester groups and the like.
  • X is a chain hydrocarbon group or alicyclic hydrocarbon having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, which may have a substituent.
  • An organic group selected from a group, an aromatic hydrocarbon group and a heterocyclic group. Examples of the organic group include, for example, a methylene group, an ethylene group, a propylene group, a hexylene group, a cyclobutylene group, a cyclohexane group, a xylene group, a phenylene group, a thiazole group, a thiadiazole group, and a pyridylnaphthylene group.
  • Etc is a chain hydrocarbon group or alicyclic hydrocarbon having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, which may have a substituent.
  • An organic group selected from a group, an aromatic hydrocarbon group and a heterocyclic group. Examples of the organic group include, for
  • X When X is a chain hydrocarbon group or an alicyclic hydrocarbon group, X has a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in its carbon chain. Alternatively, it may have an alkyl group such as methyl or ethyl, a halogen group such as promo or black mouth, a hydroxyl group, a strong oxyl group, or an ester group.
  • the disulfide amine salt compound (I) is a disulfide compound having a carboxylic acid in one molecule represented by the formula (II) (wherein X is as defined above) and an amine of the formula (III) (wherein R,, R 2 and R 3 are as defined above) wear.
  • This reaction does not require an oxidant or a catalyst, and can be carried out with an appropriate solvent (eg, aliphatic alcohols such as methanol, ethanol, and propanol, ethers such as jetyl ether and tetrahydrofuran, acetone, It can be produced by mixing and reacting the compounds of the formula (II) and the formula (III) in ketones such as Yunon.
  • an appropriate solvent eg, aliphatic alcohols such as methanol, ethanol, and propanol, ethers such as jetyl ether and tetrahydrofuran, acetone
  • (1) is obtained by reacting a thiol compound (IV) containing a carboxylic acid in one molecule with an amine (III) in the presence of an oxidizing agent. Can be manufactured.
  • ammine (III) is stoichiometrically excessive (for example, from 1.01 to 1) relative to disulfide compound (II) or thiol compound (IV). 1 5 equivalents).
  • carboxylic acid-containing disulfide compound (II) used as the starting material in the reaction formula (1) include, for example, dithiodiglycolic acid, dithiodipropionic acid, dithiosalicylic acid, dithiobis (2-nitro). Benzoic acid).
  • reaction formula (1) examples include, for example, dithiodiglycolic acid, dithiodipropionic acid, dithiosalicylic acid, dithiobis (2-nitro).
  • Examples of the thiol compound represented by the formula (IV) used in (2) include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, and thionicotinic acid.
  • specific examples of the amine represented by the above formula (III) include, for example, methylamine, ethylamine, propylamine, ptylamine, hexylamine, isoptylamine, tert-ptylamine, dimethylamine, jetylamine, dipropylamine, diisopropylamine, cyclohexane.
  • the oxidizing agent that can be used in the reaction formula (2) is not particularly limited, but includes the following compounds. Chlorates such as sodium chlorate, potassium chlorate, and ammonium chlorate; Perchlorates such as sodium perchlorate and potassium perchlorate; Lithium peroxide, sodium peroxide Inorganic peroxides such as sodium and potassium peroxide; Chlorites such as sodium chlorite and potassium chlorite; Bromates such as sodium bromate and potassium bromate; Nitrate such as sodium nitrate, nitrate power, ammonium nitrate; iodates such as sodium iodate, calcium iodate, calcium iodate; potassium permanganate, sodium permanganate Permanganates such as sodium; dichromates such as sodium dichromate and potassium dichromate; periodates such as sodium periodate; Periodic acid such as uric acid; Chromium oxide such as chromic anhydride (chromium trioxide); Lead oxide such as lead dioxide; Iodine oxide such as
  • sodium chlorate, sodium perchlorate, sodium peroxide, sodium chlorite, hydrogen peroxide, iodine, copper ethylenediaminetetraacetate are easy to react and highly efficient.
  • Solvents that can be used for the reaction include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, ethers such as jetyl ether, tetrahydrofuran (THF), isopropyl ether, acetone, Examples include ketones such as 2-butaneone, organic organic solvents such as acetonitrile and dimethylformamide (DMF). These solvents may be used alone or in the form of a mixed solvent. Of these, aliphatic alcohols, ethers, and ketones are preferred because of their high solubility in disulfides, thiols and amines, and easy removal from the reaction product.
  • aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, and butanol
  • ethers such as jetyl ether, tetrahydrofuran (THF), isopropyl ether, acetone
  • ketones such
  • the reaction temperature of the reaction is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C. Below 0 ° C, reaction times are slow, and at temperatures above 100 ° C, undesirable side reactions of the product may occur.
  • the reaction temperature is more preferably in the range of 20 ° C to 70 ° C.
  • Vulcanizing agent ingredients that can be included in the rubber vulcanizing compound according to the present invention
  • examples of the body include sulfur, organic peroxides, quinone metal oxides, and alkylphenol monoaldehyde resins.
  • the rubber vulcanizing binder that can be used in combination with the disulfide ammine salt according to the present invention preferably contains a sulfenamide or thiuram vulcanization accelerator.
  • a sulfenamide-based or thiuram-based vulcanization accelerator By using a sulfenamide-based or thiuram-based vulcanization accelerator, vulcanization of the rubber component can be further promoted, and physical properties of the resulting vulcanized rubber can be further improved.
  • sulfenamide-based vulcanization accelerators include N-cyclohexyl 1-2 benzothiazolyl sulfenamide, N 1 t-butyl-2-benzothiazolyl sulfenamide, N— Examples include oxydiethylene-2-benzothiazolylsulfenamide and N, N'-dicyclohexyl-2-benzothiazolylsulfenamide.
  • Thiuram-based vulcanization accelerators include, for example, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethyl thiuram disulfide, tetradicyl thiuram disulfide, teramethyl thiuram monosulfide. Tetrapentyl thiuram disulfide and dipentamethyl thiuram disulfide.
  • the rubber composition of the present invention comprises an unvulcanized rubber component selected from the group consisting of a gen-based rubber and a halogenated rubber and the disulfide amine salt (I) according to the present invention.
  • the unvulcanized rubber component that can be contained in the rubber composition is selected from the group consisting of Gen rubber and halogenated rubber.
  • Gen rubber include natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene butadiene copolymer rubber, ethylene propylene gen copolymer rubber, acrylonitrile.
  • One butadiene copolymer rubber may be mentioned.
  • halogenated rubber examples include, for example, brominated butyl rubber, chlorine Halogenated butyl rubber such as butylated rubber, isoprene-paramethylstyrene copolymer halide (eg brominated), chlorobrene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, chlorinated Acrylic rubber, fluororubber, epoxidized acrylic rubber, and acrylic rubber copolymerized with halogen monomers.
  • brominated butyl rubber such as butylated rubber, isoprene-paramethylstyrene copolymer halide (eg brominated), chlorobrene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, chlorinated Acrylic rubber, fluororubber, epoxidized acrylic rubber, and acrylic rubber copolymerized with hal
  • the disulfide ammine salt (I) according to the present invention is generally used alone or in the art as a vulcanizing agent or accelerator for unvulcanized rubber. It can be used as a compounding agent for rubber vulcanization together with a vulcanizing agent or a vulcanization accelerator.
  • the amine salt (I) of the disulfide of the present invention has a desired vulcanization and / or vulcanization acceleration effect and heat resistance without interfering with the vulcanization and / or vulcanization acceleration action of the disulfide amine salt (I).
  • the normal vulcanization temperature is preferably from 140 ° C to 200 ° C.
  • reinforcing agents such as carbon black and silica usually blended in the rubber composition, vulcanization or crosslinking agent, vulcanization or crosslinking accelerator, stearin Vulcanization accelerators such as acids, zinc oxide and magnesium oxide, various oils, anti-aging agents, fillers, softeners such as paraffin oil, various compounding agents and additives such as plasticizers and anti-aging agents General amount in general usage depending on application You may mix
  • Such blending can be blended by kneading with a general-purpose rubber kneader such as a roll, a Banbury mixer, a kneader or the like.
  • the rubber component blended as the component (A) in the rubber composition of the present invention comprises at least 30 parts by weight of natural rubber (NR) and / or polyisoprene rubber (IR) in 100 parts by weight of gen-based rubber. Preferably, 40 to 90 parts by weight are blended. If the blending amount of N R and / or I R is small, the strength is insufficient, which is not preferable. As another gen-based rubber that can be used in the present invention, any gen-based rubber that can be blended in the rubber composition for tires can be used.
  • the amine salt compound of the carboxylic acid-containing disulfide of the formula (I) is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight per 100 parts by weight of the gen-based rubber. Blend 5 parts by weight. If the compounding amount of the carboxylic acid-containing disulfide amine salt compound (I) is small, the hardness is insufficient, which is not preferable. Conversely, if the compounding amount is large, the elongation at break is insufficient.
  • the vulcanization accelerator used in the rubber composition of the present invention comprises only the amine salt compound (I) of the carboxylic acid-containing disulfide
  • the vulcanization accelerator is used in addition to the amine salt compound of the carboxylic acid-containing disulfide. It may include those generally used as vulcanization accelerators for unvulcanized rubber in the technical field.
  • the carboxylic acid-containing disulfide amine salt compound of the present invention can be used in other vulcanization accelerators as long as the desired vulcanization acceleration effect can be achieved without impeding the vulcanization acceleration action of the carboxylic acid-containing disulfide amine salt compound. It can be used in any proportion with respect to the total amount of agent.
  • a sulfenamide-based, thiuram-based or thiazol-based vulcanization accelerator may be used in combination as other vulcanization accelerators, such as sulfenamide-based, thiuram-based or thiazole.
  • a system vulcanization accelerator By using a system vulcanization accelerator, vulcanization of the rubber component can be further accelerated.
  • sulfenamide-based vulcanization accelerators include:
  • thiuram vulcanization accelerators include tetrakis (2-ethylhexyl) thiuram disulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, and tetrabendiyl.
  • Examples include thiuram disulfide and dipentamethylene thiuram tetrasulfide.
  • thiol-based vulcanization accelerators include 2-mercaptobenzothiazol and dibenzothiazyl disulfide.
  • the rubber composition of the present invention has an iodine adsorption amount of 70 to 1 as component (C). 4 0 (g / kg), preferably 7 5 ⁇ 1 3 0 (g / kg), and DBP absorption 6 0 ⁇ 1 8 0 (1 0- 5 m 3 / kg), preferably 6 5-1
  • 6 0 (1 0 " 5 m 3 / kg) force pump rack with 20 to 80 parts by weight, preferably 30 to 70 parts by weight per 100 parts by weight of rubber component (A)
  • the iodine adsorption amount (measured in accordance with JISK 6 2 1 7 — 1) of the carbon black to be used is small, it is not preferable because the strength of the rubber is insufficient, and conversely if it is large, the heat generation deteriorates.
  • the DBP absorption amount measured in accordance with JISK 6 2 1 7-4) is small, it is not preferable because the hardness is insufficient, and conversely if it is large, the elong
  • an organic metal salt as the component (D) is used as the metal content, and the rubber component (A) is 0.05 to 0.5 parts by weight, preferably 0, per 100 parts by weight. Add 1 to 0.4 parts by weight. If the blending amount is small, the bonding performance with the metal belt is insufficient, which is not preferable. Conversely, if the blending amount is large, the fatigue resistance becomes insufficient.
  • the organometallic salt that can be used in the present invention nickel (N i) or cobalt (C o) salt is preferably used. Specifically, nathem nickel (Ni content 20% by Nippon Kagaku Sangyo) Nikko Materials Co., Ltd. Cobalt Naphthenate (Co content: 10%), Rhodia Manopond (Co content: 22%), Nippon Kagaku Sangyo Co., Ltd. o Content 1 6.5 5%) can be used.
  • the rubber composition according to the present invention includes a reinforcing agent such as silica (a filler), a vulcanization or cross-linking agent, various oils, an anti-aging agent, a plasticizer, and other tires.
  • a reinforcing agent such as silica (a filler), a vulcanization or cross-linking agent, various oils, an anti-aging agent, a plasticizer, and other tires.
  • Various additives that are generally blended for rubber compositions can be blended, and such additives can be blended with general-purpose rubber kneaders such as rolls, Banbury mixers, kneaders, etc. in a general manner. Use, knead to make a composition, vulcanize or crosslink Can be used for
  • the blending amounts of these additives can be conventional conventional blending amounts as long as they are not contrary to the purpose of the present invention.
  • the rubber composition according to the present invention can be suitably used for the belt coating rubber and belt edge cushion of a typical
  • Dithiosalicylic acid 3 0 6.4 g (1 mo 1) and cyclohexylamine 2 18.2 g (2.2 mol) were added in methanol 100 g and reacted at room temperature for 30 minutes. . After completion of the reaction, methanol was removed under reduced pressure, followed by filtration. After washing twice with acetone and drying, 49.9.2 g (yield: 99%) of white powder of compound A represented by the following formula was obtained. .
  • Bead stearic acid YR (manufactured by NOF Corporation)
  • Jinhua stamp fine sulfur (Tsurumi Chemical Co., Ltd.)
  • Noxeller CZ— G N-cyclohexyl 1-2-benzothiazolylsulfenamide (Ouchi Shinsei Chemical)
  • Noxeller DM—P Dibenzothiazyl disulfide (Ouchi Shinsei Chemical)
  • Mooney For unvulcanized rubber composition, Mooney using L type low evening, preheating time 1 minute, test temperature 1 25 ° C according to JISK 6 3 0 0 — 1 9 9 4 The viscosity was measured continuously. The minimum value of the Mooney viscosity was designated as V B. Moreover, Mooney viscosity was measured beam one Nice coach time to 5 points increases from V n. The results are shown in Table I 1-2.
  • the Mooney scorch time is a scorch (rubber burn) index, and a longer one is preferable.
  • each of the obtained rubber compositions was vulcanized at 150 ° C. for 30 minutes to prepare a vulcanized sheet of 15 cm ⁇ I 5 cm ⁇ 2 mm.
  • J I S 3 dumbbell-shaped specimens are punched from this vulcanized sheet, and J I S
  • the obtained rubber composition was vulcanized in a predetermined mold at 150 ° C. for 30 minutes to prepare a test sample, and physical properties of the vulcanized rubber were measured by the following test methods. The results are shown in Table II-1I.
  • Elongation at break Based on JI S K 6 25 1, a dumbbell No. 3 sample was stretched at a speed of 500 mm / min, and the elongation at break at 20 ° C was measured. The results were expressed as an index with the value of Comparative Example II-1 as 1 0 0. The larger the value, the higher the elongation.
  • Adhesion test In accordance with the AS TM D 1 8 7 1 C method, the peel force required when a 25 mm wide test piece was peeled at a speed of 50 O mm / min was measured. The results were expressed as an index with the value of Comparative Example II-1 as 1 0 0. The larger this value, the higher the adhesive strength.
  • Ichisu preparative KH iodine adsorption amount 9 0 cm 3/1 0 0 g, DBP absorption amount 1 1 9 X 1 0 one 5 m 3 / kg
  • Zinc flower 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.
  • Stearic acid manufactured by Nippon Oil & Fats Co., Ltd. Bead stearic acid
  • Cobalt salt Manopond made by Rhodia (Co content: 22%) (Chemical formula: (C 9 H 19 Co O) 3 B)
  • Vulcanization accelerator 1 Noxeller DZ—G vulcanization accelerator manufactured by Ouchi Shinsei Chemical Co., Ltd. 2 Noxeller DM—P 0 manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Vulcanization accelerator 3 Compound A synthesized in Preparation Example 1 Industrial applicability
  • the disulfide amine salt compound (I) of the present invention has a high vulcanization-promoting effect with respect to gen-based rubbers, halogenated butyl rubbers, and the like, and also with respect to halogenated butyl rubbers. Also acts as a vulcanizing agent.
  • a vulcanized rubber obtained by vulcanizing an unvulcanized rubber composition containing the disulfide ammine chloride compound (I) of the present invention contains a conventional vulcanizing agent and / or a vulcanization accelerator. It exhibits higher heat aging resistance than that obtained from the unvulcanized rubber composition.
  • the amine salt compound of carboxylic acid-containing disulfide is used as a vulcanization accelerator in the gen-based rubber, and specific carbon black and metal salt are added.

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Abstract

Compounds of carboxylated disulfide amine salt represented by the formula: (I) (wherein each of R1, R2 and R3 independently is hydrogen or a C1-C20 organic group optionally having a heteroatom and/or substituent; and X is a C2-C20 organic group optionally having a heteroatom and/or substituent). Further, there is provided a process for producing them and provided a rubber composition containing any thereof so as to realize enhancements of vulcanization rate and vulcanized rubber properties without detriment to scorch time. Still further, there is provided a rubber composition for tire comprising 100 parts by weight of diene rubber (A) containing at least 30 parts by weight of natural rubber and/or polyisoprene rubber; 0.1 to 5 parts by weight of compound of carboxylated disulfide amine salt (B) represented by the formula (I); 20 to 80 parts by weight of carbon black (C) of 70 to 140 (g/kg) iodine adsorption and 60 to 180 (10-5 m3/kg) DBP absorption; and 0.05 to 0.5 part by weight, in terms of metal content, of organometallic salt (D) so as to improve the adhesive performance to metal belt and low heat build-up. Still further, there is provided a pneumatic tire making use of the rubber composition for tire in its belt coating rubber and/or belt edge cushion.

Description

カルボン酸含有ジスルフィ ドのアミン塩化合物及びその製造方法並 びにそれを含むゴム組成物並びにそれをベルトコート用ゴム及び/ 又はベルトエッジクッショ ンに用いた空気入りタイヤ Amine salt compound of carboxylic acid-containing disulfide, production method thereof, rubber composition containing the same, and pneumatic tire using the same for belt coat rubber and / or belt edge cushion
技術分野 Technical field
明  Light
本発明は、 新規なカルボン酸含有ジスルフィ ドのアミン塩化合物 田  The present invention relates to a novel carboxylic acid-containing disulfide amine salt compound.
(以下、 単にジスルフィ ドのァミン塩ということがある） 及びその 製造方法並びにそれを含むゴム組成物に関する。 本発明は、 また、 タイヤ用ゴム組成物並びにそれを用いた空気入りタイヤに関し、 更 に詳しくは金属ベルトとの接着性能及び低発熱性が改良されたタイ ャ用ゴム組成物並びにそれをベルトコート用ゴム及び z又はベル卜 エッジクッショ ンに用いた空気入りタイヤに関する。  The present invention relates to a disulfide ammine salt (hereinafter sometimes referred to as a disulfide ammine salt), a production method thereof, and a rubber composition containing the same. The present invention also relates to a rubber composition for a tire and a pneumatic tire using the same, more specifically, a rubber composition for a tire with improved adhesion performance to a metal belt and low heat build-up, and a belt coat thereof. This relates to pneumatic tires used for rubber and z or bell edge cushions.
背景技術 Background art
一般的に、 ゴムの加硫促進剤として、 チウラム系、 スルフェンァ ミ ド系、 メルカプトべンゾチアゾール系などが用いられている。 ス ルフェンアミ ド系は遅効性促進剤であり、 加硫中に熱により N— S 結合が解離し、 メルカプトべンゾチアゾ一ルとァミンを再生すると されている。 再生されるメルカプトべンゾチアゾ一ルは加硫促進剤 として働き、 アミンは亜鉛華に配位することで加硫系の活性化及び に加硫中間体との反応などにより加硫反応を促進する重要な役割を 果たすことが知られている （Chapman, A. V. , Porter, M. ： "Sulphu r Vulcanization Chemistry" in the Natural Rubber Science and Technology Roberts, A. D. Ed. , Oxford Science Publications, London (1988).参照） 。 これに対してジスルフィ ド系加硫剤であるジベンゾチアゾールジ スルフイ ドは熱により S — S結合が解離し、 メルカプトべンゾチア ゾールを再生するが、 ァミンによる加硫活性能力がないため、 加硫 が遅く、 加硫促進能力においてスルフェンアミ ド類に劣っていると いわれている。 ジベンゾチアゾ一ルジスルフィ ドの加硫促進能力を 改善する目的でアミン類を併用することは考えられるが、 その場合 は遊離アミンの反応性が高いために、 低温においても硫黄などの加 硫剤と反応することでスコーチ時間に悪影響を及ぼすという問題が ある。 Generally, thiuram, sulfenamide, and mercaptobenzothiazole are used as rubber vulcanization accelerators. Sulfenamides are slow-acting accelerators, and N—S bonds are dissociated by heat during vulcanization, and mercaptobenzothiazoles and amines are regenerated. Regenerated mercaptobenzothiazol acts as a vulcanization accelerator, and amine coordinates with zinc white to promote the vulcanization reaction by activating the vulcanization system and reacting with vulcanization intermediates. (See Chapman, AV, Porter, M .: "Sulphur Vulcanization Chemistry" in the Natural Rubber Science and Technology Roberts, AD Ed., Oxford Science Publications, London (1988).) . In contrast, dibenzothiazole disulfide, a disulfide-based vulcanizing agent, dissociates S — S bonds by heat and regenerates mercaptobenzothiazole. It is late and is said to be inferior to sulfenamides in terms of vulcanization acceleration ability. Although it is conceivable to use amines together to improve the vulcanization promoting ability of dibenzothiazol disulfide, in that case, the reactivity of free amines is high, so it reacts with vulcanizing agents such as sulfur even at low temperatures. This has the problem of adversely affecting the scorch time.
空気入りタイヤにおいて金属製のベルトとゴムとの接着性能は、 タイヤが複合材である観点からも重要であることはいうまでもなく 、 この接着性能が低いとタイヤセパレ一シヨンなどの故障につなが ることになる。 その対策として、 コバルト （C o ) 塩の配合や加硫 促進剤の変更によって接着反応を優位にする手法が試みられている が （日本ゴム協会誌 6 5巻及び 7 0頁 （ 1 9 9 2年） 参照） 発熱性 が悪化するという問題がある。 発明の開示  Needless to say, the adhesion performance between a metal belt and rubber in a pneumatic tire is also important from the viewpoint that the tire is a composite material. If this adhesion performance is low, failure such as tire separation will occur. It will be. As a countermeasure, a method has been tried to make the adhesion reaction superior by changing the blending of cobalt (C o) salt and vulcanization accelerator (Volumes 6 5 and 7 0 (1 9 9 2 (Refer to year)) There is a problem that exothermicity deteriorates. Disclosure of the invention
従って、 本発明はスコーチ時間に悪影響を及ぼすことなく、 加硫 速度及び加硫ゴム物性の改善が可能なカルボン酸含有ジスルフィ ド のァミン塩化合物及びその製造方法並びにそれを含むゴム組成物を 提供することを目的にする。  Therefore, the present invention provides a carboxylic acid-containing disulfide ammine salt compound capable of improving the vulcanization speed and physical properties of the vulcanized rubber without adversely affecting the scorch time, a process for producing the same, and a rubber composition containing the same. To aim.
本発明は、 また、 上記カルボン酸含有ジスルフイ ドのアミン塩を 含むゴム組成物を提供することを目的とする。  Another object of the present invention is to provide a rubber composition containing an amine salt of the carboxylic acid-containing disulfide.
本発明は、 更に、 空気入りタイヤのベルトコート用ゴム及び 又 はベルトエッジクッショ ンなどに使用するのに適した、 金属ベル卜 との接着性能及び低発熱性が改良されたゴム組成物並びにそれを用 いた空気入りタイヤを提供することを目的とする。 The present invention further relates to a rubber composition improved in adhesion performance to metal bells and low heat generation suitable for use in a rubber for belt coating of a pneumatic tire and / or a belt edge cushion. For An object of the present invention is to provide a pneumatic tire.
本発明に従えば、 式 （ I ) ：
Figure imgf000006_0001
According to the present invention, the formula (I):
Figure imgf000006_0001
"00C-X-S-S-X-C00"  "00C-X-S-S-X-C00"
(式中、 , R2 及び R3 は、 独立に、 水素又は炭素数 1〜 2 0 のへテロ原子及び Z又は置換基を有してもよい有機基であり、 Xは 炭素数 2〜 2 0のへテロ原子及び/又は置換基を有してもよい有機 基である。 ） (In the formula, each of R 2 and R 3 is independently hydrogen or an organic group which may have a hetero atom having 1 to 20 carbon atoms and Z or a substituent, and X is an organic group having 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
で表されるカルボン酸含有ジスルフィ ドのァミン塩化合物が提供さ れる。 A carboxylic acid-containing disulfide ammine salt compound represented by the formula:
本発明に従えば、 また、 式 （II) で表わされる 1つの分子にカル ボン酸を有するジスルフィ ド化合物と式 （III) で表わされるアミ ンとを反応させて式 （ I ) で表されるカルボン酸含有ジスルフイ ド のァミン塩化合物を製造する方法が提供される。  According to the present invention, a molecule represented by the formula (II) is reacted with a disulfide compound having a carboxylic acid and an amine represented by the formula (III). Provided is a method for producing a carboxylic acid-containing disulfide ammine salt compound.
反応式 （ 1 ) Reaction formula (1)
H00C-X-S-S-X-C00H + R3 H00C-XSSX-C00H + R 3
Figure imgf000006_0002
Figure imgf000006_0002
(式中、 , R2 及び R3 は、 独立に、 水素又は炭素数 1〜 2 0 のへテロ原子及び Z又は置換基を有してもよい有機基であり、 Xは 炭素数 2〜 2 0のへテロ原子及び/又は置換基を有してもよい有機 基である。 ） 本発明に従えば、 更に、 式 （IV) で表わされる 1つの分子にカル ボン酸を有するチオール化合物と式 （III) で表わされるァミンと を酸化剤の存在下で反応させて式 （ I ) で表されるカルボン酸含有 ジスルフィ ドのアミン塩化合物を製造する方法が提供される。 (In the formula, each of R 2 and R 3 is independently hydrogen or an organic group which may have a hetero atom having 1 to 20 carbon atoms and Z or a substituent, and X is an organic group having 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent. According to the present invention, a thiol compound having a carboxylic acid in one molecule represented by the formula (IV) and an amine represented by the formula (III) are further reacted in the presence of an oxidizing agent to form the formula (I) A method for producing an amine salt compound of a carboxylic acid-containing disulfide represented by the formula:
反応式 （2) Reaction formula (2)
Figure imgf000007_0001
Figure imgf000007_0001
(IV) (III) ( I ) (IV) (III) (I)
(式中、 ， R2 及び R3 は、 独立に、 水素又は炭素数 1〜 2 0 のへテロ原子及び/又は置換基を有してもよい有機基であり、 Xは 炭素数 2〜 2 0のへテロ原子及び/又は置換基を有してもよい有機 基である。 ） (Wherein, R 2 and R 3 are independently hydrogen or an organic group optionally having 1 to 20 carbon atoms and / or a substituent, and X is 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
本発明に従えば、 更に、 また （A) 天然ゴム （N R) 及び/又は ポリイソプレンゴム （ I R) を少なく とも 3 0重量部以上含むジェ ン系ゴム 1 0 0重量部、  According to the present invention, furthermore, (A) Geno rubber containing 100 parts by weight or more of natural rubber (N R) and / or polyisoprene rubber (IR) at least 30 parts by weight,
(B) 前記式 （ I ) で表されるカルボン酸含有ジスルフィ ドのァ ミン塩化合物 0. 1〜 5重量部、  (B) 0.1-5 parts by weight of an amine salt compound of a carboxylic acid-containing disulfide represented by the formula (I)
(C) よう素吸着量が 7 0〜： L 4 0 ( g /kg) 、 D B P吸収量が 6 0〜： L 8 0 ( 1 0— 5m3/kg) のカーボンブラック 2 0〜 8 0重 量部並びに (C) Iodine adsorption amount 7 0~: L 4 0 (g / kg), DBP absorption amount 6 0~: L 8 0 (1 0- 5 m 3 / kg) Carbon black 2 0-8 0 Weight section and
(D) 有機金属塩を金属含有量として 0. 0 5〜 0. 5重量部 を含んでなるタイヤ用ゴム組成物並びにそれをベルトコート用ゴム 及びノ又はベルトエッジクッションに用いた空気入りタイヤが提供 される。 本発明によれば、 前記式 （ I ) のジスルフイ ドのアミン塩を用い ることにより、 ジェン系ゴムやハロゲン化ブチルゴムなどに対して 高い加硫促進効果を有し、 更にスコーチ時間に悪影響を及ぼすこと なく、 加硫速度及び加硫ゴム物性 （例えば耐熱老化性） を改善する ことができる。 本発明によれば、 また、 カルボン酸含有ジスルフィ ドのアミン塩化合物を加硫促進剤としてゴム組成物に配合すること により、 空気入りタイヤの金属ベルトとの接着性能の向上と低発熱 性との両立を可能にすることができる。 図面の簡単な説明 (D) A rubber composition for a tire comprising 0.05 to 0.5 parts by weight of an organic metal salt as a metal content, and a pneumatic tire using the rubber composition for a belt coat rubber and a belt edge cushion. Provided. According to the present invention, by using the amine salt of the disulfide of the above formula (I), it has a high vulcanization acceleration effect on a gen-based rubber, a halogenated butyl rubber and the like, and further adversely affects the scorch time. Therefore, the vulcanization speed and physical properties of vulcanized rubber (for example, heat aging resistance) can be improved. According to the present invention, by adding an amine salt compound of carboxylic acid-containing disulfide to a rubber composition as a vulcanization accelerator, the adhesion performance with a metal belt of a pneumatic tire is improved and low heat build-up is achieved. Coexistence can be made possible. Brief Description of Drawings
図 1 は本発明に係るゴム組成物を用いるベルト及び Z又はベルト エッジクッショ ンを他の部位と共に模式的に示す典型的な空気入り タイヤの子午線半断面図である。 発明を実施するための最良の形態  FIG. 1 is a meridian half cross-sectional view of a typical pneumatic tire schematically showing a belt and a Z or belt edge cushion using the rubber composition according to the present invention together with other portions. BEST MODE FOR CARRYING OUT THE INVENTION
本発明に係るカルボン酸含有ジスルフィ ドのァミン塩化合物 （即 ち本発明のジスルフイ ドのアミン塩） は、 前記式 （ I ) で表わされ る化合物である。  The amine salt compound of carboxylic acid-containing disulfide (that is, the amine salt of disulfide of the present invention) according to the present invention is a compound represented by the above formula (I).
前記式 （ I ) において、 ， R 2 及び R 3 は、 それぞれ独立に 、 水素又は炭素数 1 〜 2 0、 好ましくは炭素数 1 〜 1 2の有機基で あることができ、 そのような有機基としては、 例えばメチル基、 ェ チル基、 プロピル基、 ブチル基、 へキシル基、 ステアリル基などの 鎖式炭化水素基、 シクロプロピル基、 シクロブチル基、 シクロへキ シル基などの環式炭化水素基が挙げられる。 それら有機基の鎖内に 、 窒素原子、 酸素原子、 硫黄原子などのへテロ原子を有していても よい。 そのような有機基の例としては、 例えば、 メ トキシプロピル 基、 メ トキシェチル基、 テトラヒ ドロフルフリル基、 ヒ ドロキシェ チル基、 ヒ ドロキシシクロへキシル基等が挙げられる。 R , 及び R 2 は、 それらが結合している窒素原子と共に、 複素環基、 例えばィ ミダゾール基、 トリアゾ一ル基、 ピラゾール基、 アジリジン基、 ピ 口リジン基、 ピぺリジン基、 モルホリン基、 チアモルホリン基等の 基を形成していてもよい。 R , 及び R 2 がそれらが結合している窒 素原子と共に複素環基を形成している場合には、 さらにその複素環 上に置換基を有していてもよい。 この置換基の例としては、 例えば メチル、 ェチルなどのアルキル基 ； ブロモ、 クロ口などのハロゲン 基 ； ヒ ドロキシル基、 アルコキシ基、 カルボキシル基、 エステル基 等が挙げられる。 In the formula (I),, R 2 and R 3 can each independently be hydrogen or an organic group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. For example, a chain hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a stearyl group, and a cyclic hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group Is mentioned. The organic group chain may have a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of such an organic group include, for example, a methoxypropyl group, a methoxetyl group, a tetrahydrofurfuryl group, a hydroxete Examples thereof include a til group and a hydroxycyclohexyl group. R, and R 2 together with the nitrogen atom to which they are attached, a heterocyclic group such as an imidazole group, a triazol group, a pyrazole group, an aziridine group, a pi-lysine group, a piperidine group, a morpholine group, A group such as a thiamorpholine group may be formed. When R 1 and R 2 form a heterocyclic group together with the nitrogen atom to which they are bonded, they may further have a substituent on the heterocyclic ring. Examples of this substituent include, for example, alkyl groups such as methyl and ethyl; halogen groups such as bromo and black mouth; hydroxyl groups, alkoxy groups, carboxyl groups, ester groups and the like.
前記式 （ I ) において、 Xは、 置換基を有していてもよい炭素数 2〜 2 0 の、 好ましくは炭素数 2〜 1 2 の、 鎖式炭化水素基もしく は脂環式炭化水素基、 芳香族炭化水素基及び複素環基から選ばれる 有機基である。 この有機基の例としては、 例えば、 メチレン基、 ェ チレン基、 プロピレン基、 へキシレン基、 シクロブチレン基、 シク 口へキシレン基、 フエ二レン基、 チアゾール基、 チアジアゾール基 、 ピルジルナフチレン基等が挙げられる。 Xが鎖式炭化水素基又は 脂環式炭化水素基である場合には、 Xは、 その炭素鎖内に、 窒素原 子、 酸素原子、 硫黄原子から成る群から選ばれるヘテロ原子を有し ていてもよく、 メチル、 ェチルなどのアルキル基、 プロモ、 クロ口 などのハロゲン基、 ヒ ドロキシル基、 力ルポキシル基、 エステル基 などを有してもよい。  In the above formula (I), X is a chain hydrocarbon group or alicyclic hydrocarbon having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, which may have a substituent. An organic group selected from a group, an aromatic hydrocarbon group and a heterocyclic group. Examples of the organic group include, for example, a methylene group, an ethylene group, a propylene group, a hexylene group, a cyclobutylene group, a cyclohexane group, a xylene group, a phenylene group, a thiazole group, a thiadiazole group, and a pyridylnaphthylene group. Etc. When X is a chain hydrocarbon group or an alicyclic hydrocarbon group, X has a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in its carbon chain. Alternatively, it may have an alkyl group such as methyl or ethyl, a halogen group such as promo or black mouth, a hydroxyl group, a strong oxyl group, or an ester group.
本発明に係るジスルフイ ドのアミン塩化合物 （ I ) は、 前記反応 式 （ 1 ) に示すように、 前記式 （I I ) で示される 1 つの分子にカル ボン酸を有するジスルフィ ド化合物 （式中、 Xは前記定義の通りで ある） と前記式 （I I I ) のァミン類 （式中、 R , , R 2 及び R 3は前 記定義の通りである） とを反応させることにより製造することがで きる。 この反応には酸化剤や触媒などを必要とすることなく、 適当 な溶媒 （例えばメタノール、 エタノール、 プロパノールなどの脂肪 族アルコール、 ジェチルエーテル、 テトラヒ ドロフランなどのェ一 テル類、 アセトン、 2—ブ夕ノンなどのケトン類など） 中で式 （II ) 及び式 （III) の化合物を混合反応させることによって、 製造す ることができる。 As shown in the reaction formula (1), the disulfide amine salt compound (I) according to the present invention is a disulfide compound having a carboxylic acid in one molecule represented by the formula (II) (wherein X is as defined above) and an amine of the formula (III) (wherein R,, R 2 and R 3 are as defined above) wear. This reaction does not require an oxidant or a catalyst, and can be carried out with an appropriate solvent (eg, aliphatic alcohols such as methanol, ethanol, and propanol, ethers such as jetyl ether and tetrahydrofuran, acetone, It can be produced by mixing and reacting the compounds of the formula (II) and the formula (III) in ketones such as Yunon.
本発明の別の態様によれば、 前記ジスルフィ ドのァミン塩化合物 According to another aspect of the present invention, the disulfide ammine salt compound
( 1 ) は、 前記反応式 （ 2 ) に示すように、 1つの分子にカルボン 酸を含有するチオール化合物 （IV) とァミン （III) との反応を酸 化剤の存在下で反応させることによって製造することができる。 As shown in the reaction formula (2), (1) is obtained by reacting a thiol compound (IV) containing a carboxylic acid in one molecule with an amine (III) in the presence of an oxidizing agent. Can be manufactured.
前記反応式 （ 1 ) 及び （ 2 ) において、 ァミン （III) は、 ジス ルフィ ド化合物 （II) 又はチオール化合物 （IV) に対して、 化学量 論的に過剰量 （例えば 1 . 0 1〜 1. 1 5当量） で反応させるのが 好ましい。  In the reaction formulas (1) and (2), ammine (III) is stoichiometrically excessive (for example, from 1.01 to 1) relative to disulfide compound (II) or thiol compound (IV). 1 5 equivalents).
前記反応式 （ 1 ) において、 出発原料として用いられるカルボン 酸含有ジスルフイ ド化合物 （II) の具体例としては、 例えば、 ジチ ォジグリコール酸、 ジチォジプロピオン酸、 ジチォサリチル酸、 ジ チォビス （ 2 —ニトロ安息香酸） などがあげられる。 一方、 反応式 Specific examples of the carboxylic acid-containing disulfide compound (II) used as the starting material in the reaction formula (1) include, for example, dithiodiglycolic acid, dithiodipropionic acid, dithiosalicylic acid, dithiobis (2-nitro). Benzoic acid). On the other hand, reaction formula
( 2 ) で用いられる式 （IV) で表わされるチオール化合物としては メルカプト酢酸、 2 —メルカプトプロピオン酸、 3 —メルカプトプ ロピオン酸、 チォサリチル酸、 チォニコチン酸などがあげられる。 一方、 上記式 （III) で表されるァミンの具体例としては、 例え ば、 メチルァミン、 ェチルァミン、 プロピルァミン、 プチルァミン 、 へキシルァミン、 イソプチルァミン、 t e r t —プチルァミン， ジメチルァミン、 ジェチルァミン、 ジプロピルアミン、 ジイソプロ ピルァミン、 シクロプロピルァミン、 シクロブチルァミン、 シクロ へキシルァミン、 N—メチルシクロへキシルァミン、 N—ェチルシ クロへキシルァミン、 ジシクロへキシルァミ ン、 2 —メチルシクロ へキシルァミ ン、 e x o _ 2 —ァミノ ノルポルナン、 2 —メ トキシ ェチルァミ ン、 ビス （ 2 —メ トキシェチル） ァミ ン、 テトラフルフ リルァミン、 モルホリ ン、 チオモルホリ ン、 1 —メチルビペラジン 、 2 —メチルイミダゾール、 エタノールァミ ン、 2—アミ ノシクロ へキサノール、 ピぺラジン、 2 —ピぺラジンメタノール、 2 —ピぺ ラジンエタノール、 1 一 （ 2 —ヒ ドロキシェチル） ピぺラジン、 ト リ メチルァミ ン、 トリェチルァミン、 ト リプロピルァミ ンなどが挙 げられる。 Examples of the thiol compound represented by the formula (IV) used in (2) include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, and thionicotinic acid. On the other hand, specific examples of the amine represented by the above formula (III) include, for example, methylamine, ethylamine, propylamine, ptylamine, hexylamine, isoptylamine, tert-ptylamine, dimethylamine, jetylamine, dipropylamine, diisopropylamine, cyclohexane. Propylamine, cyclobutylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylyl Chlorohexamine, dicyclohexylamine, 2—methylcyclohexylamine, exo _ 2 —amino norpolnan, 2 — methoxyethylamine, bis (2-methoxychetil) amine, tetrafurfurylamine, morpholine, thiomorpholine, 1-methylbiperazine, 2-methylimidazole, ethanolamine, 2-aminocyclohexanol, piperazine, 2-piperazinemethanol, 2-piperazineethanol, 1 (2-hydroxetyl) piperazine, to Examples include limethylamine, triethylamine, and tripropylamine.
前記反応式 （ 2 ) に使用することができる酸化剤としては、 特に 制限はないが、 次の化合物が挙げられる。 塩素酸ナ ト リウム、 塩素 酸カ リ ウム、 塩素酸アンモニゥムなどの塩素酸塩類 ； 過塩素酸ナト リ ウム、 過塩素酸カ リ ゥムなどの過塩素酸塩類 ； 過酸化リチウム、 過酸化ナト リ ウム、 過酸化カ リウムなどの無機過酸化物 ； 亜塩素酸 ナ ト リ ウム、 亜塩素酸カリゥムなどの亜塩素酸塩類 ； 臭素酸ナ ト リ ゥム、 臭素酸カ リウムなどの臭素酸塩類 ； 硝酸ナ トリ ウム、 硝酸力 リ ウム、 硝酸アンモニゥムなどの硝酸塩類 ； ヨウ素酸ナト リ ウム、 ヨウ素酸カ リ ウム、 ヨウ素酸カルシウムなどのヨウ素酸塩類 ； 過マ ンガン酸カ リ ウム、 過マンガン酸ナ ト リ ウムなどの過マンガン酸塩 類 ； 重クロム酸ナトリ ウム、 重クロム酸カ リ ウムなどの重クロム酸 塩類 ； 過ヨウ素酸ナト リ ウムなどの過ヨウ素酸塩類 ； メタ過ヨウ素 酸などの過ヨウ素酸 ； 無水クロム酸 （三酸化クロム） などのクロム 酸化物 ； 二酸化鉛などの鉛酸化物 ； 五酸化二ヨウ素などのヨウ素酸 化物 ； 亜硝酸ナ トリウム、 亜硝酸カ リ ゥムなどの亜硝酸塩類 ； 次亜 塩素酸カルシウムなどの次亜塩素酸塩類 ； 三塩素化イソシァヌル酸 などの塩素化イソシァヌル酸 ； ペルォキソ二硫酸アンモニゥムなど のペルォキソ二硫酸塩類 ； ペルォキソホウ酸アンモニゥムなどのぺ ルォキソホウ酸塩類 ； 過塩素酸 ； 過酸化水素 ； 硝酸 ； フッ化塩素、 三フッ化臭素、 五フッ化臭素、 五フッ化ヨウ素、 ヨウ素などのハロ ゲン化化合物 ； エチレンジアミンテトラ酢酸銅、 二 トリ 口 トリプロ ピオン酸銅などの銅の水溶性キレ一 ト化合物 ； ジメチルスルホキシ ドなどの有機化合物 ； 酸素など。 酸化剤として酸素を使用する場合 、 酸素源として空気を用いることもできる。 これらは単独で用いて もよく、 危険のない限り複数を組合せて用いてもよい。 これらのう ち、 反応が容易で効率が高い点で、 塩素酸ナト リウム、 過塩素酸ナ ト リ ウム、 過酸化ナト リ ウム、 亜塩素酸ナト リウム、 過酸化水素、 ヨウ素、 エチレンジアミンテトラ酢酸銅、 二ト リ 口 トリプロピオン 酸銅および酸素が好ましい。 The oxidizing agent that can be used in the reaction formula (2) is not particularly limited, but includes the following compounds. Chlorates such as sodium chlorate, potassium chlorate, and ammonium chlorate; Perchlorates such as sodium perchlorate and potassium perchlorate; Lithium peroxide, sodium peroxide Inorganic peroxides such as sodium and potassium peroxide; Chlorites such as sodium chlorite and potassium chlorite; Bromates such as sodium bromate and potassium bromate; Nitrate such as sodium nitrate, nitrate power, ammonium nitrate; iodates such as sodium iodate, calcium iodate, calcium iodate; potassium permanganate, sodium permanganate Permanganates such as sodium; dichromates such as sodium dichromate and potassium dichromate; periodates such as sodium periodate; Periodic acid such as uric acid; Chromium oxide such as chromic anhydride (chromium trioxide); Lead oxide such as lead dioxide; Iodine oxide such as diiodine pentoxide; Sodium nitrite, nitrous acid Nitrites such as humic acid; Hypochlorites such as calcium hypochlorite; Chlorinated isocyanuric acid such as trichlorinated isocyanuric acid; Peroxodisulfates such as ammonium peroxodisulfate; Pemonic acid such as ammonium peroxoborate Peroxo acids; Hydrogen peroxide; Nitric acid; Halogenated compounds such as chlorine fluoride, bromine trifluoride, bromine pentafluoride, iodine pentafluoride and iodine; Copper ethylenediaminetetraacetate, Nitri-Tripro Copper-soluble water-soluble chelate compounds such as copper pionate; Organic compounds such as dimethyl sulfoxide; If oxygen is used as the oxidant, air can also be used as the oxygen source. These may be used alone or in combination as long as there is no danger. Of these, sodium chlorate, sodium perchlorate, sodium peroxide, sodium chlorite, hydrogen peroxide, iodine, copper ethylenediaminetetraacetate are easy to react and highly efficient. Preferred are copper tripropionate and oxygen.
前記反応に用いることができる溶媒としては、 メタノール、 エタ ノール、 プロパノール、 イソプロパノール、 ブタノールなどの脂肪 族アルコール、 ジェチルェ一テル、 テ トラヒ ドロフラン （T H F ) 、 イソプロピルエーテルなどのェ一テル類、 アセ トン、 2 —ブ夕ノ ンなどのケ トン類、 ァセ トニ ト リル、 ジメチルホルムアミ ド （D M F ) などの含室素有機溶媒などがあげられる。 これらの溶媒は単独 または混合溶媒の形で使用しても良い。 これらのうち、 ジスルフィ ド類、 チオール類とアミ ン類への溶解性が高く、 反応生成物から取 り除きやすい点から、 脂肪族アルコール類、 エーテル類、 ケトン類 が好ましい。  Solvents that can be used for the reaction include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, ethers such as jetyl ether, tetrahydrofuran (THF), isopropyl ether, acetone, Examples include ketones such as 2-butaneone, organic organic solvents such as acetonitrile and dimethylformamide (DMF). These solvents may be used alone or in the form of a mixed solvent. Of these, aliphatic alcohols, ethers, and ketones are preferred because of their high solubility in disulfides, thiols and amines, and easy removal from the reaction product.
前記反応の反応温度には特に限定はないが、 0 °C〜 1 0 0 °Cの範 囲内であることが好ましい。 0 °C未満では反応時間が遅くなり、 1 0 0 °Cを超える温度では生成物の望ましくない副反応が起こるおそ れがある。 この反応温度は、 さ らに好ましくは 2 0 °C〜 7 0 °Cの範 囲内である。  The reaction temperature of the reaction is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C. Below 0 ° C, reaction times are slow, and at temperatures above 100 ° C, undesirable side reactions of the product may occur. The reaction temperature is more preferably in the range of 20 ° C to 70 ° C.
本発明に係るゴム加硫用配合剤に含めることのできる加硫剤の具 体例としては、 例えば、 硫黄、 有機過酸化物、 キノ ン 金属酸化物、 及びアルキルフヱノ一ルーホルムアルデヒ ド樹脂等が 挙げられる。 Vulcanizing agent ingredients that can be included in the rubber vulcanizing compound according to the present invention Examples of the body include sulfur, organic peroxides, quinone metal oxides, and alkylphenol monoaldehyde resins.
本発明に係るジスルフイ ドのァミン塩と併用できるゴム加硫用配 合剤としては、 スルフェンアミ ド系又はチウラム系の加硫促進剤を 含むことが好ましい。 スルフェンアミ ド系又はチウラム系の加硫促 進剤を用いることにより、 ゴム成分の加硫をさ らに促進し、 また、 得られる加硫ゴムの物性をさらに向上させることができる。 スルフ ェンアミ ド系の加硫促進剤としては、 例えば、 N—シクロへキシル 一 2 一べンゾチアゾリルスルフェンアミ ド、 N一 t ―ブチル - 2 - ベンゾチアゾリルスルフェンアミ ド、 N—ォキシジエチレン一 2— ベンゾチアゾリルスルフェンアミ ド、 N , N ' ージシクロへキシル — 2 —ベンゾチアゾリルスルフェンアミ ドが挙げられる。 チウラム 系の加硫促進剤としては、 例えば、 テ トラキス （ 2 —ェチルへキシ ル） チウラムジスルフィ ド、 テトラメチルチウラムジスルフィ ド、 テ トラェチルチウラムジスルフィ ド、 テ卜ラメチルチウラムモノス ルフィ ド、 テトラべンジルチウラムジスルフィ ド、 ジペンタメチレ ンチウラムテ卜ラスルフィ ドが挙げられる。  The rubber vulcanizing binder that can be used in combination with the disulfide ammine salt according to the present invention preferably contains a sulfenamide or thiuram vulcanization accelerator. By using a sulfenamide-based or thiuram-based vulcanization accelerator, vulcanization of the rubber component can be further promoted, and physical properties of the resulting vulcanized rubber can be further improved. Examples of sulfenamide-based vulcanization accelerators include N-cyclohexyl 1-2 benzothiazolyl sulfenamide, N 1 t-butyl-2-benzothiazolyl sulfenamide, N— Examples include oxydiethylene-2-benzothiazolylsulfenamide and N, N'-dicyclohexyl-2-benzothiazolylsulfenamide. Thiuram-based vulcanization accelerators include, for example, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethyl thiuram disulfide, tetradicyl thiuram disulfide, teramethyl thiuram monosulfide. Tetrapentyl thiuram disulfide and dipentamethyl thiuram disulfide.
本発明のゴム組成物は、 ジェン系ゴム及びハロゲン化ゴムから成 る群から選ばれる未加硫ゴム成分と本発明に係るジスルフィ ドのァ ミ ン塩 （ I ) を含む。 このゴム組成物が含むことができる未加硫ゴ ム成分としてはジェン系ゴム及びハロゲン化ゴムから成る群から選 ばれる。 ジェン系ゴムの具体例としては、 例えば天然ゴム、 ブ夕ジ ェンゴム、 イソプレンゴム、 クロロプレンゴム、 スチレン一ブ夕ジ ェン共重合体ゴム、 エチレン一プロピレン一ジェン共重合体ゴム、 アク リ ロニト リル一ブタジエン共重合体ゴムが挙げられる。 また、 ハロゲン化ゴムの具体例としては、 例えば臭素化ブチルゴム、 塩素 化ブチルゴム等のハロゲン化ブチルゴム、 イソプチレン—パラメチ ルスチレン共重合体のハロゲン化物 （例えば臭素化物） 、 クロロブ レンゴム、 ェピクロロヒ ドリンゴム、 クロロスルホン化ポリエチレ ン、 塩素化ポリエチレン、 マレイン酸変性塩素化ポリエチレン、 塩 素化アクリルゴム、 フッ素ゴム、 エポキシ化アクリルゴム、 ハロゲ ン系モノマーを共重合させたアクリルゴムが挙げられる。 The rubber composition of the present invention comprises an unvulcanized rubber component selected from the group consisting of a gen-based rubber and a halogenated rubber and the disulfide amine salt (I) according to the present invention. The unvulcanized rubber component that can be contained in the rubber composition is selected from the group consisting of Gen rubber and halogenated rubber. Specific examples of the Gen rubber include natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene butadiene copolymer rubber, ethylene propylene gen copolymer rubber, acrylonitrile. One butadiene copolymer rubber may be mentioned. Specific examples of halogenated rubber include, for example, brominated butyl rubber, chlorine Halogenated butyl rubber such as butylated rubber, isoprene-paramethylstyrene copolymer halide (eg brominated), chlorobrene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, chlorinated Acrylic rubber, fluororubber, epoxidized acrylic rubber, and acrylic rubber copolymerized with halogen monomers.
本発明に係るゴム組成物において、 本発明に従ったジスルフィ ド のァミン塩 （ I ) は単独又は当該技術分野において未加硫ゴムの加 硫剤又は加硫促進剤として一般的に使用されている加硫剤又は加硫 促進剤と共にゴム加硫用配合剤として使用できる。 本発明のジスル フイ ドのアミン塩 （ I ) は、 当該ジスルフイ ドのアミン塩 （ I ) の 加硫及び/又は加硫促進作用を妨げずに所望の加硫及び/又は加硫 促進効果並びに耐熱老化性の向上を達成できる限り、 当該ゴム加硫 用配合剤に含まれる他の加硫剤及び/又は加硫促進剤の合計量に対 して、 任意の割合で使用することができる。 しかしながら、 望まし い加硫及び 又は加硫促進効果を達成するには、 ジェン系ゴム及び ハロゲン化ゴムから成る群から選ばれる未加硫ゴム成分 1 0 0重量 部に対して 0 . 1〜 2 0重量部であるのが好ましい'。 前記ジスルフ ィ ドのァミン塩 （ I ) の配合量がこの範囲内であると、 実用的な強 度及びゴム弾性を発現できるなどのより有利な効果が得られる。 ま た、 加硫温度は通常の 1 4 0 °C〜 2 0 0 °Cが好ましい。  In the rubber composition according to the present invention, the disulfide ammine salt (I) according to the present invention is generally used alone or in the art as a vulcanizing agent or accelerator for unvulcanized rubber. It can be used as a compounding agent for rubber vulcanization together with a vulcanizing agent or a vulcanization accelerator. The amine salt (I) of the disulfide of the present invention has a desired vulcanization and / or vulcanization acceleration effect and heat resistance without interfering with the vulcanization and / or vulcanization acceleration action of the disulfide amine salt (I). As long as improvement in aging can be achieved, it can be used in an arbitrary ratio with respect to the total amount of other vulcanizing agents and / or vulcanization accelerators contained in the compounding agent for rubber vulcanization. However, in order to achieve a desired vulcanization and / or vulcanization acceleration effect, 0.1 to 2 parts per 100 parts by weight of an unvulcanized rubber component selected from the group consisting of a gen-based rubber and a halogenated rubber It is preferably 0 parts by weight. When the amount of the disulfide ammine salt (I) is within this range, more advantageous effects such as practical strength and rubber elasticity can be obtained. Further, the normal vulcanization temperature is preferably from 140 ° C to 200 ° C.
本発明のゴム組成物には、 上記加硫促進剤の他に、 ゴム組成物に 通常配合されるカーボンブラックやシリカ等の補強剤、 加硫又は架 橋剤、 加硫又は架橋促進剤、 ステアリン酸や酸化亜鉛及び酸化マグ ネシゥムなどの加硫促進助剤、 各種オイル、 老化防止剤、 充填剤、 パラフィ ンオイル等の軟化剤、 可塑剤、 老化防止剤等の各種配合剤 及び添加剤を、 各種用途に応じて一般的に使用される量で一般的な 配合方法によって配合してよい。 かかる配合は、 汎用のゴム用混練 機、 例えばロール、 バンバリ一ミキサー、 ニーダ一等で混練するこ とにより配合できる。 In the rubber composition of the present invention, in addition to the above vulcanization accelerator, reinforcing agents such as carbon black and silica usually blended in the rubber composition, vulcanization or crosslinking agent, vulcanization or crosslinking accelerator, stearin Vulcanization accelerators such as acids, zinc oxide and magnesium oxide, various oils, anti-aging agents, fillers, softeners such as paraffin oil, various compounding agents and additives such as plasticizers and anti-aging agents General amount in general usage depending on application You may mix | blend by the compounding method. Such blending can be blended by kneading with a general-purpose rubber kneader such as a roll, a Banbury mixer, a kneader or the like.
本発明者らは、 前記課題を解決すべく研究を進めた結果、 力ルポ ン酸含有ジスルフィ ドのァミン塩化合物を加硫促進剤として、 ゴム 成分、 特定のカーボンブラック及び有機金属塩と共に、 ゴム組成物 中に配合することによって、 タイヤの金属ベルトとの接着性能の向 上と低発熱性との両立を可能にすることに成功した。  As a result of advancing research to solve the above-mentioned problems, the present inventors have found that rubber compounds, specific carbon blacks and organometallic salts are used as rubber accelerators, disulfide-containing amine compounds containing strong sulfonic acids, and rubbers. By blending in the composition, we succeeded in achieving both improved adhesion performance of tires to metal belts and low heat build-up.
本発明のゴム組成物に成分 （A ) として配合されるゴム成分は、 ジェン系ゴム 1 0 0重量部中に天然ゴム （N R ) 及び/又はポリイ ソプレンゴム （ I R ) を少なく とも 3 0重量部以上、 好ましくは 4 0〜 9 0重量部を配合する。 N R及び/又は I Rの配合量が少ない と強度が不足するので好ましくない。 本発明において使用すること のできる他のジェン系ゴムとしては、 タイヤ用ゴム組成物に配合す ることができる任意のジェン系ゴムを用いることができ、 具体的に はブタジエンゴム、 クロロプレンゴム、 スチレン一ブタジエン共重 合体ゴム、 エチレン一プロピレン一ジェン共重合体ゴム、 ァクリ ロ 二トリル一ブタジエン共重合体ゴムなどをあげることができる。 本発明によれば、 前記式 （ I ) のカルボン酸含有ジスルフイ ドの アミン塩化合物を、 ジェン系ゴム 1 0 0重量部当り、 0 . 1〜 5重 量部、 好ましくは 0 . 3〜4 . 5重量部配合する。 このカルボン酸 含有ジスルフイ ドのアミン塩化合物 （ I ) の配合量が少ないと硬度 が不足するので好ましくなく、 逆に多いと破断伸びが不足するので 好ましくない。  The rubber component blended as the component (A) in the rubber composition of the present invention comprises at least 30 parts by weight of natural rubber (NR) and / or polyisoprene rubber (IR) in 100 parts by weight of gen-based rubber. Preferably, 40 to 90 parts by weight are blended. If the blending amount of N R and / or I R is small, the strength is insufficient, which is not preferable. As another gen-based rubber that can be used in the present invention, any gen-based rubber that can be blended in the rubber composition for tires can be used. Specifically, butadiene rubber, chloroprene rubber, styrene Examples thereof include monobutadiene copolymer rubber, ethylene monopropylene monogen copolymer rubber, acrylic nitrile monobutadiene copolymer rubber, and the like. According to the present invention, the amine salt compound of the carboxylic acid-containing disulfide of the formula (I) is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight per 100 parts by weight of the gen-based rubber. Blend 5 parts by weight. If the compounding amount of the carboxylic acid-containing disulfide amine salt compound (I) is small, the hardness is insufficient, which is not preferable. Conversely, if the compounding amount is large, the elongation at break is insufficient.
本発明のゴム組成物において使用する加硫促進剤は前記カルボン 酸含有ジスルフイ ドのアミン塩化合物 （ I ) のみから成っていても 、 そのカルボン酸含有ジスルフィ ドのァミン塩化合物に加えて当該 技術分野において未加硫ゴムの加硫促進剤として一般的に使用され ているものを含むものであってもよい。 本発明のカルポン酸含有ジ スルフィ ドのアミン塩化合物は、 当該カルボン酸含有ジスルフィ ド のアミン塩化合物の加硫促進作用を妨げずに所望の加硫促進効果を 達成できる限り、 他の加硫促進剤の合計量に対して、 任意の割合で 使用することができる。 Even if the vulcanization accelerator used in the rubber composition of the present invention comprises only the amine salt compound (I) of the carboxylic acid-containing disulfide, the vulcanization accelerator is used in addition to the amine salt compound of the carboxylic acid-containing disulfide. It may include those generally used as vulcanization accelerators for unvulcanized rubber in the technical field. The carboxylic acid-containing disulfide amine salt compound of the present invention can be used in other vulcanization accelerators as long as the desired vulcanization acceleration effect can be achieved without impeding the vulcanization acceleration action of the carboxylic acid-containing disulfide amine salt compound. It can be used in any proportion with respect to the total amount of agent.
本発明に係るゴム組成物には、 他の加硫促進剤として例えばスル フェンアミ ド系、 チウラム系又はチアゾ一ル系の加硫促進剤を併用 してもよく、 スルフェンアミ ド系、 チウラム系又はチアゾール系の 加硫促進剤を用いることにより、 ゴム成分の加硫をさらに促進する ことができる。 スルフェンアミ ド系の加硫促進剤としては、 例えば In the rubber composition according to the present invention, for example, a sulfenamide-based, thiuram-based or thiazol-based vulcanization accelerator may be used in combination as other vulcanization accelerators, such as sulfenamide-based, thiuram-based or thiazole. By using a system vulcanization accelerator, vulcanization of the rubber component can be further accelerated. Examples of sulfenamide-based vulcanization accelerators include:
、 N—シクロへキシル— 2—べンゾチアゾリルスルフェンアミ ド、 N— t —プチル— 2—べンゾチアゾリルスルフェンアミ ド、 N—ォ キシジエチレン一 2—ベンゾチアゾリルスルフェンアミ ド、 N , N ' ージシクロへキシル— 2 —べンゾチアゾリルスルフェンアミ ドが 挙げられる。 チウラム系の加硫促進剤としては、 例えばテトラキス ( 2 —ェチルへキシル） チウラムジスルフィ ド、 テトラメチルチウ ラムジスルフィ ド、 テ卜ラエチルチウラムジスルフィ ド、 テトラメ チルチウラムモノスルフィ ド、 テトラべンジルチウラムジスルフィ ド、 ジペンタメチレンチウラムテトラスルフィ ドが挙げられる。 チ ァゾ一ル系の加硫促進剤としては、 2—メルカプトべンゾチアゾー ル、 ジベンゾチアジルジスルフィ ドが挙げられる。 N-cyclohexyl-2-benzothiazolylsulfenamide, N-t-butyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfene Amide, N, N'-dicyclohexyl-2-benzothiazolylsulfenamide. Examples of thiuram vulcanization accelerators include tetrakis (2-ethylhexyl) thiuram disulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, and tetrabendiyl. Examples include thiuram disulfide and dipentamethylene thiuram tetrasulfide. Examples of thiol-based vulcanization accelerators include 2-mercaptobenzothiazol and dibenzothiazyl disulfide.
本発明に係るゴム組成物に含めることのできる加硫剤の具体例と しては、 例えば、 硫黄、 有機過酸化物、 キノンジォキシム、 金属酸 化物、 及びアルキルフエノ一ルーホルムアルデヒ ド樹脂等が挙げら れる。  Specific examples of the vulcanizing agent that can be included in the rubber composition according to the present invention include, for example, sulfur, organic peroxide, quinone dioxime, metal oxide, and alkylphenol aldehyde resin. .
本発明のゴム組成物は成分 （C ) としてよう素吸着量が 7 0〜 1 4 0 ( g /kg) 、 好ましくは 7 5〜 1 3 0 ( g /kg) 、 そして D B P吸収量が 6 0〜 1 8 0 ( 1 0— 5m3/kg) 、 好ましくは 6 5〜 1 6 0 ( 1 0 "5m3 /kg) の力一ポンプラックをゴム成分 （A) 1 0 0重量部当り、 2 0〜 8 0重量部、 好ましくは 3 0〜 7 0重量部配 合する。 使用するカーボンブラックのよう素吸着量 （ J I S K 6 2 1 7 — 1 に準拠して測定） が小さいとゴムの強度が不足するの で好ましくなく、 逆に大きいと発熱が悪化するので好ましくない。 また力一ポンブラックの D B P吸収量 （ J I S K 6 2 1 7 - 4 に準拠して測定） が小さいと硬度が不足するので好ましくなく、 逆 に大きいと破断伸びが不足するので好ましくない。 The rubber composition of the present invention has an iodine adsorption amount of 70 to 1 as component (C). 4 0 (g / kg), preferably 7 5~ 1 3 0 (g / kg), and DBP absorption 6 0~ 1 8 0 (1 0- 5 m 3 / kg), preferably 6 5-1 Combine 6 0 (1 0 " 5 m 3 / kg) force pump rack with 20 to 80 parts by weight, preferably 30 to 70 parts by weight per 100 parts by weight of rubber component (A) If the iodine adsorption amount (measured in accordance with JISK 6 2 1 7 — 1) of the carbon black to be used is small, it is not preferable because the strength of the rubber is insufficient, and conversely if it is large, the heat generation deteriorates. Also, if the DBP absorption amount (measured in accordance with JISK 6 2 1 7-4) is small, it is not preferable because the hardness is insufficient, and conversely if it is large, the elongation at break is insufficient.
本発明のゴム組成物には、 成分 （D) として有機金属塩を金属含 有量としてゴム成分 （A) 1 0 0重量部当り、 0. 0 5〜 0. 5重 量部、 好ましくは 0. 1〜 0. 4重量部配合する。 この配合量が少 ないと金属ベルトとの接着性能が不足するので好ましくなく、 逆に 多いと耐疲労性が不十分となるので好ましくない。 本発明において 使用することができる有機金属塩としては、 ニッケル （N i ) 、 コ バルト （C o ) 塩の使用が好ましく、 具体的には日本化学産業製ナ ーセムニッケル （N i含有率 2 0. 0 4 %) 、 日鉱マテリアルズ社 製ナフテン酸コバルト （C o含有率 1 0 %) 、 ローディア社製マノ ポンド （C o含有率 2 2 %) 、 日本化学産業製ナ一セム第ニコバル ト （C o含有率 1 6. 5 4 %) などを用いることができる。  In the rubber composition of the present invention, an organic metal salt as the component (D) is used as the metal content, and the rubber component (A) is 0.05 to 0.5 parts by weight, preferably 0, per 100 parts by weight. Add 1 to 0.4 parts by weight. If the blending amount is small, the bonding performance with the metal belt is insufficient, which is not preferable. Conversely, if the blending amount is large, the fatigue resistance becomes insufficient. As the organometallic salt that can be used in the present invention, nickel (N i) or cobalt (C o) salt is preferably used. Specifically, nathem nickel (Ni content 20% by Nippon Kagaku Sangyo) Nikko Materials Co., Ltd. Cobalt Naphthenate (Co content: 10%), Rhodia Manopond (Co content: 22%), Nippon Kagaku Sangyo Co., Ltd. o Content 1 6.5 5%) can be used.
本発明に係るゴム組成物には、 前記した成分に加えて、 シリカな どの補強剤 （フイ ラ一） 、 加硫又は架橋剤、 各種オイル、 老化防止 剤、 可塑剤などのタイヤ用、 その他のゴム組成物用に一般的に配合 されている各種添加剤を配合することができ、 かかる添加剤は一般 的な方法で汎用のゴム用混練機、 例えばロール、 バンバリ一ミキサ 一、 ニーダ一等を用いて、 混練して組成物とし、 加硫又は架橋する のに使用することができる。 これらの添加剤の配合量は本発明の目 的に反しない限り、 従来の一般的な配合量とすることができる。 本発明に係るゴム組成物は図 1 に模式的に示す典型的な空気入り タイヤのベルトコート用ゴム及びベルトエッジクッッシヨ ンに好適 に用いることができ、 従来の一般的な空気入りタイヤの製造ライン にそのまま使用することができる。 実施例 In addition to the components described above, the rubber composition according to the present invention includes a reinforcing agent such as silica (a filler), a vulcanization or cross-linking agent, various oils, an anti-aging agent, a plasticizer, and other tires. Various additives that are generally blended for rubber compositions can be blended, and such additives can be blended with general-purpose rubber kneaders such as rolls, Banbury mixers, kneaders, etc. in a general manner. Use, knead to make a composition, vulcanize or crosslink Can be used for The blending amounts of these additives can be conventional conventional blending amounts as long as they are not contrary to the purpose of the present invention. The rubber composition according to the present invention can be suitably used for the belt coating rubber and belt edge cushion of a typical pneumatic tire schematically shown in FIG. It can be used directly on the production line. Example
以下に示す実施例及び比較例を参照して本発明をさらに詳しく説 明するが、 本発明の技術的範囲は、 これらの実施例によって限定さ れるものでないことは言うまでもない。  The present invention will be described in more detail with reference to the following examples and comparative examples, but it goes without saying that the technical scope of the present invention is not limited by these examples.
調製例 1 ： ジスルフィ ドのァミン塩化合物 Aの合成 ：  Preparation Example 1: Synthesis of disulfide ammine compound A:
メタノール 1 0 0 0 g中、 ジチォサリチル酸 3 0 6. 4 g ( 1 mo 1) とシクロへキシルァミン 2 1 8. 2 g ( 2. 2 mol) を入れ、 室 温で 3 0分反応させた。 反応終了後、 減圧下でメタノールを除いて からろ過し、 アセトンで 2回洗浄 · 乾燥後、 下記式で示される白色 粉末の化合物 Aを 4 9 9. 2 g (収率 9 9 %) 得た。  Dithiosalicylic acid 3 0 6.4 g (1 mo 1) and cyclohexylamine 2 18.2 g (2.2 mol) were added in methanol 100 g and reacted at room temperature for 30 minutes. . After completion of the reaction, methanol was removed under reduced pressure, followed by filtration. After washing twice with acetone and drying, 49.9.2 g (yield: 99%) of white powder of compound A represented by the following formula was obtained. .
Figure imgf000018_0001
Figure imgf000018_0001
(化合物 A) (Compound A)
' HNMR ( 4 0 0 MHz, DM S O - d 6 ) δ i n p p m ： 1. 0 - 1. 3， 1. 5 , 1. 7， 1. 9 , 2. 9 , 7. 1 , 7. 2 , 7. 5 , 7. 8 元素分析値 （％) ： C 2 6 H 3 6 N 2 0 4 S 2 'HNMR (400 MHz, DM SO -d 6) δ inppm: 1.0-1. 3, 1.5, 1.7, 1.9, 2.9, 7.1, 7.2, 7 .5, 7.8 Elemental analysis (%): C 2 6 H 3 6 N 2 0 4 S 2
計算値 ： C， 6 1. 8 7 ； H, 7. 1 9 ； N, 5. 5 5 ； S , 1 2 . 7 1 Calculated values: C, 6 1. 8 7; H, 7. 19; N, 5.5 5; S, 1 2. 7 1
測定値 ： C , 6 1. 5 4 ； H, 7. 2 8 ； N , 5. 5 6 ； S , 1 2 . 7 2 Measurements: C, 6 1.54; H, 7.28; N, 5.56; S, 12.77
調製例 2 ： ジスルフィ ドのァミン塩化合物 Bの合成 ：  Preparation Example 2: Synthesis of disulfide ammine salt compound B:
チォサリチル酸 3 0 8. 4 g ( 2 mol) とシクロへキシルァミン 2 1 8. 2 g ( 2. 2 mol) をイソプロピルアルコール 1 0 0 0 g 中、 エチレンジァミン四酢酸ニナトリウム銅四水和物 7. 5 g ( 0 Thiosalicylic acid 3 08.4 g (2 mol) and cyclohexylamine 2 1 8.2 g (2.2 mol) in isopropyl alcohol 1 00 0 0 g in ethylene diamine tetraacetate disodium copper tetrahydrate 7. 5 g (0
. 8 mol%) を入れ、 酸素雰囲気下、 5 0 °Cで 3時間反応させた。 反応終了後、 ろ過乾燥し、 下記式で示される'化合物 Bを 4 7 9. 0 g (収率 9 5 %) 得た。 8 mol%) and allowed to react at 50 ° C for 3 hours in an oxygen atmosphere. After completion of the reaction, the product was filtered and dried to obtain 4 79.0 g (yield 95%) of Compound B represented by the following formula.
Figure imgf000019_0001
Figure imgf000019_0001
(化合物 B) 調製例 3 ： ジスルフィ ドのァミン塩化合物 Cの合成 (Compound B) Preparation Example 3: Synthesis of disulfide amine salt compound C
3， 3 ' —ジチォジプロピオン酸 2 1 0. 3 g ( 1 mol) とシク 口へキシルァミン 2 1 8. 2 g ( 2. 2 mol) をメタノール 1 0 0 0 g中、 室温で 3 0分反応させた。 反応終了後、 減圧下でメタノー ルを除いてからろ過し、 アセトンで 2回洗浄 · 乾燥後、 下記式で示 される白色粉末の化合物 Cを 4 0 0. 4 g (収率 9 8 %) 得た。
Figure imgf000020_0001
3, 3 '— Dithiodipropionic acid 2 1 0. 3 g (1 mol) and hexylamine 2 1 8. 2 g (2.2 mol) in methanol at 100 0 g at room temperature It was made to react for minutes. After completion of the reaction, methanol was removed under reduced pressure, followed by filtration, washing twice with acetone and drying, and then 40.04 g (yield: 98%) of white powdered compound C represented by the following formula: Obtained.
Figure imgf000020_0001
(化合物 C)(Compound C)
1 H NM R ( 4 0 0 MHz, DM S O— d 6 ) <5 i n p p m : 1. 1 - 1. 2 , 1 . 5， 1. 7， 1. 9 , 2. 3， 2. 8， 2. 9 元素分析値 （％) ： C 1 8 H 3 6 N 2 0 4 S 2 1 H NM R (400 MHz, DM SO— d 6) <5 inppm: 1. 1-1.2, 1.5, 1.7, 1.9, 2.3, 2.8, 2. 9 Elemental analysis (%): C 1 8 H 3 6 N 2 0 4 S 2
計算値 ： C， 5 2. 9 1 ； H, 8. 8 8 ； N, 6. 8 6 ； S , 1 5 . 6 9 Calculated values: C, 5 2. 9 1; H, 8. 8 8; N, 6. 8 6; S, 1 5. 6 9
測定値 ： C， 5 2. 8 3 ； H, 9. 0 3 ； N, 6. 8 4 ； S , 1 5 . 9 2 Measured value: C, 5 2.83; H, 9.03; N, 6.84; S, 15.99.2
実施例 I 一 1〜 I — 3及び比較例 I — 1〜 I 一 3  Example I 1 1 to I 3 and Comparative Example I 1 1 to I 1 3
ゴム組成物の調製  Preparation of rubber composition
下記表 I 一 1 に示す配合成分を 1. 7 リ ツ トルのバンバリ一ミキ サ一により 5分間混合して均一に分散させ、 各実施例及び比較例の ゴム組成物を得た。 得られた各実施例及び比較例のゴム組成物を下 記の各試験法により評価した。 結果を表 I 一 1 に示す。 The compounding ingredients shown in Table I 1-1 were mixed for 5 minutes with a 1.7-liter Banbury mixer, and dispersed uniformly to obtain rubber compositions of Examples and Comparative Examples. The obtained rubber compositions of Examples and Comparative Examples were evaluated by the following test methods. The results are shown in Table I 1-1.
表 I— 1 ：ゴム組成物の配合 Table I-1: Compounding of rubber composition
Figure imgf000021_0001
表 I一 1脚注
Figure imgf000021_0001
Table I One footnote
1) RSS#3  1) RSS # 3
2) Exxon Broiobutyl 2255 (日本ブチル製）  2) Exxon Broiobutyl 2255 (Nippon Butyl)
3) ダイアブラック E (三菱化学製）  3) Dia Black E (Mitsubishi Chemical)
4) 酸化亜鉛 3種 （正同化学製）  4) Zinc oxide 3 types (manufactured by Shodo Chemical)
5) ビーズステアリン酸 YR (日本油脂製）  5) Bead stearic acid YR (manufactured by NOF Corporation)
6) ノクラック 6C (大内新興化学製）  6) Nocrack 6C (Ouchi Shinsei Chemical)
7) ハイレッツ G— 100X (三井化学製）  7) Hilets G— 100X (Mitsui Chemicals)
8) デゾレックス 3号 （昭和シェル石油製）  8) Desolex No. 3 (made by Showa Shell Sekiyu)
9) 金華印微粉硫黄 （鶴見化学工業製）  9) Jinhua stamp fine sulfur (Tsurumi Chemical Co., Ltd.)
10) ノクセラー CZ— G (N—シクロへキシル一2—ベンゾチアゾリルスルフェンアミド) (大内新興化学製）  10) Noxeller CZ— G (N-cyclohexyl 1-2-benzothiazolylsulfenamide) (Ouchi Shinsei Chemical)
11) ノクセラー DM— P (ジベンゾチアジルジスルフイド） （大内新興化学製）  11) Noxeller DM—P (Dibenzothiazyl disulfide) (Ouchi Shinsei Chemical)
12) ジチォサリチル酸 （関東化学製） 試験法  12) Dithiosalicylic acid (manufactured by Kanto Chemical) test method
ムーニースコ一チ  Mooney
未加硫のゴム組成物について、 J I S K 6 3 0 0 — 1 9 9 4の 規定に準じて、 L形ロー夕を使用し、 予熱時間 1分、 試験温度 1 2 5 °Cの条件で、 ムーニー粘度を連続的に測定した。 ム一ニー粘度の 最低値を VBとした。 また、 ムーニー粘度が Vnから 5ポイン ト上昇 するまでのム一ニースコーチ時間を測定した。 結果を表 I 一 2 に示 す。 ムーニースコーチ時間は、 スコーチ （ゴム焼け） の指標であり 、 長い方が好ましい。 For unvulcanized rubber composition, Mooney using L type low evening, preheating time 1 minute, test temperature 1 25 ° C according to JISK 6 3 0 0 — 1 9 9 4 The viscosity was measured continuously. The minimum value of the Mooney viscosity was designated as V B. Moreover, Mooney viscosity was measured beam one Nice coach time to 5 points increases from V n. The results are shown in Table I 1-2. The Mooney scorch time is a scorch (rubber burn) index, and a longer one is preferable.
次に得られた各ゴム組成物について、 1 5 0 °Cで 3 0分間加硫し て、 1 5 c m X I 5 c mX 2 mmの加硫シー トを作成した。 この加 硫シートから J I S 3号ダンベル形状の試験片を打ち抜き、 J I S Next, each of the obtained rubber compositions was vulcanized at 150 ° C. for 30 minutes to prepare a vulcanized sheet of 15 cm × I 5 cm × 2 mm. J I S 3 dumbbell-shaped specimens are punched from this vulcanized sheet, and J I S
K 6 2 5 1 に従って、 伸び 3 0 0 %時のモジュラス （M 3 0 0 ) 、 破断応力 （TB) 及び破断時伸び （EB) を求め、 さらに、 J I SAccording to K 6 2 5 1, the modulus (M 3 0 0), elongation at break (T B ), and elongation at break (E B ) at an elongation of 300% are obtained.
K 6 2 5 7に従って、 8 0 °Cで 9 6時間老化後の M 3 0 0 を測定 し、 M 3 0 0の初期値を基準として老化後の M 3 0 0の値の変化率 (%) を下記式 ： According to K 6 2 5 7, M 3 0 0 after 96 hours aging at 80 ° C was measured, and the rate of change in M 3 0 0 value after aging with reference to the initial value of M 3 0 0 (% ) With the following formula:
1 0 0 X [ (老化後の M 3 0 0 ) - (老化前の M 3 0 0 ) ] / ( 老化前の M 3 0 0 )  1 0 0 X [(M 3 0 0 after aging)-(M 3 0 0 before aging)] / (M 3 0 0 before aging)
に従って求めた。 結果を表 I 一 2に示す。 変化率の値が小さいほど 、 耐熱老化性が優れていることを示す。 表 I一 2 ：試験結果 Sought according to. The results are shown in Table I-12. The smaller the change rate value, the better the heat aging resistance. Table I 1-2: Test results
Figure imgf000022_0001
実施例 II一 ：！〜 II一 4及び比較例 II一 1〜11— 4
Figure imgf000022_0001
Example II! ~ II 1 4 and Comparative Example II 1 1-11-4
サンプルの調製 Sample preparation
表 II— I に示す配合において、 加硫促進剤と硫黄を除く成分を 1 . 7 リ ッ トルの密閉型ミキサーで 5分間混練し、 1 6 0 °Cに達した ときに放出してマスターバッチを得た。 このマスターバッチに加硫 促進剤と硫黄をオープンロールで混練し、 ゴム組成物を得た。 In the formulation shown in Table II-I, the ingredients other than the vulcanization accelerator and sulfur were kneaded for 5 minutes in a 1.7-liter closed mixer, and released when the temperature reached 160 ° C to be a master batch. Got. Vulcanize in this masterbatch An accelerator and sulfur were kneaded with an open roll to obtain a rubber composition.
次に得られたゴム組成物を所定の金型中で 1 5 0 °Cで 3 0分間加 硫して試験サンプルを調製し、 以下に示す試験法で加硫ゴムの物性 を測定した。 結果は表 II一 I に示す。  Next, the obtained rubber composition was vulcanized in a predetermined mold at 150 ° C. for 30 minutes to prepare a test sample, and physical properties of the vulcanized rubber were measured by the following test methods. The results are shown in Table II-1I.
ゴム物性評価試験法 Rubber physical property evaluation test method
破断伸び ： J I S K 6 2 5 1 に準拠しダンベル 3号型のサン プルを速度 5 0 0 mm/minで伸張し、 2 0 °Cにおける破断伸びを測 定した。 結果は比較例 II— 1の値を 1 0 0 として指数表示した。 こ の数値が大きいほど伸びが高いことを示す。  Elongation at break: Based on JI S K 6 25 1, a dumbbell No. 3 sample was stretched at a speed of 500 mm / min, and the elongation at break at 20 ° C was measured. The results were expressed as an index with the value of Comparative Example II-1 as 1 0 0. The larger the value, the higher the elongation.
発熱性 ： J I S K 6 3 9 4に準拠し、 初期歪 1 0 %、 振幅 2 %、 周波数 2 0 Hzにて 2 0 °Cにおける t a η <5 を測定した。 結果は 比較例 II一 1の値を 1 0 0 として指数表示した。 この数値が大きい ほど低発熱で発熱性が良好であることを示す。  Exothermic property: Ta η <5 at 20 ° C was measured at an initial strain of 10%, an amplitude of 2%, and a frequency of 20 Hz in accordance with JISK 6 3 94. The result was expressed as an index with the value of Comparative Example II-1 as 1 0 0. Higher values indicate lower heat generation and better heat generation.
接着試験 ： A S TM D 1 8 7 1 C法に準拠し、 2 5匪幅の試験 片を 5 0 O mm/minの速度で剥離させたときに必要な剥離力を測定 した。 結果は比較例 II— 1の値を 1 0 0 として指数表示した。 この 数値が大きいほど接着力が高いことを示す。 Adhesion test: In accordance with the AS TM D 1 8 7 1 C method, the peel force required when a 25 mm wide test piece was peeled at a speed of 50 O mm / min was measured. The results were expressed as an index with the value of Comparative Example II-1 as 1 0 0. The larger this value, the higher the adhesive strength.
表 Π— 1 Table Π— 1
Figure imgf000024_0001
Figure imgf000024_0001
表 II一 1脚注 Table II-1 Footnote
N R : 天然ゴム R S S # 3  N R: Natural rubber R S S # 3
C B ： 東海カーボン （株） 製 力一ポンプラック シ一ス ト KH ( よう素吸着量 9 0 cm3/ 1 0 0 g， D B P吸収量 1 1 9 X 1 0一5 m3 /kg) CB: Tokai Carbon Co., Ltd. force first pump racks Ichisu preparative KH (iodine adsorption amount 9 0 cm 3/1 0 0 g, DBP absorption amount 1 1 9 X 1 0 one 5 m 3 / kg)
亜鉛華 ： 正同化学工業 （株） 製 酸化亜鉛 3種 Zinc flower: 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.
ステアリ ン酸 ： 日本油脂 （株） 製 ビーズステアリ ン酸 Stearic acid: manufactured by Nippon Oil & Fats Co., Ltd. Bead stearic acid
老化防止剤 （ 6 D) ： 大内新興化学工業 （株） 製 ノクラック 2 2Anti-aging agent (6D): NOCRACK 2 2 manufactured by Ouchi Shinsei Chemical Co., Ltd.
4 Four
コバルト塩 ： ローディ ァ社製 マノポン ド （C o含有率 2 2 %) ( 化学式 ： （C9H19 C o O) 3 B) Cobalt salt: Manopond made by Rhodia (Co content: 22%) (Chemical formula: (C 9 H 19 Co O) 3 B)
硫黄 ： ァクゾノーベル （株） 製 ク リステックス H S O T 2 0 加硫促進剤 1 大内新興化学工業 （株） 製 ノクセラー D Z— G 加硫促進剤 2 大内新興化学工業 （株） 製 ノクセラー DM— P 0 加硫促進剤 3 調製例 1で合成した化合物 A 産業上の利用可能性 Sulfur: Cristex HSOT 2 manufactured by Akzo Nobel Co., Ltd. 0 Vulcanization accelerator 1 Noxeller DZ—G vulcanization accelerator manufactured by Ouchi Shinsei Chemical Co., Ltd. 2 Noxeller DM—P 0 manufactured by Ouchi Shinsei Chemical Co., Ltd. Vulcanization accelerator 3 Compound A synthesized in Preparation Example 1 Industrial applicability
以上の通り に、 本発明のジスルフイ ドのアミ ン塩化合物 （ I ) は 、 ジェン系ゴム及びハロゲン化ブチルゴムなどに対して高い加硫促 進効果を有し、 しかも、 ハロゲン化ブチルゴムに対しては、 加硫剤 としても作用する。 さ らに、 本発明のジスルフィ ドのァミン塩化合 物 （ I ) を含む未加硫ゴム組成物を加硫して得られる加硫ゴムは、 従来の加硫剤及び/又は加硫促進剤を含む未加硫ゴム組成物から得 られるものより も高い耐熱老化性を示す。 本発明では、 更に、 ジェ ン系ゴムにカルボン酸含有ジスルフィ ドのアミ ン塩化合物を加硫促 進剤として使用すると共に、 特定のカーボンブラック及び金属塩を 使用することによって、 タイヤの金属ベルトとの接着性能の向上と 低発熱性との両立を可能にしたので、 空気入りタイヤのベルトコ一 ト用ゴム及び/又はベルトエッジクッションなどのゴム組成物とし て有用である。 As described above, the disulfide amine salt compound (I) of the present invention has a high vulcanization-promoting effect with respect to gen-based rubbers, halogenated butyl rubbers, and the like, and also with respect to halogenated butyl rubbers. Also acts as a vulcanizing agent. Further, a vulcanized rubber obtained by vulcanizing an unvulcanized rubber composition containing the disulfide ammine chloride compound (I) of the present invention contains a conventional vulcanizing agent and / or a vulcanization accelerator. It exhibits higher heat aging resistance than that obtained from the unvulcanized rubber composition. In the present invention, the amine salt compound of carboxylic acid-containing disulfide is used as a vulcanization accelerator in the gen-based rubber, and specific carbon black and metal salt are added. By using it, it was possible to improve both the adhesion performance of the tire with the metal belt and the low heat build-up, so as a rubber composition for pneumatic tire belt coats and / or belt edge cushions, etc. Useful.

Claims

請 求 の 範 囲 The scope of the claims
1. 式 （ I ) ： 1. Formula (I):
(门(门
Figure imgf000027_0001
Figure imgf000027_0001
— 00C - X— S— S - X— COO—  — 00C-X— S— S — X— COO—
(式中、 ， R2 及び R3 は、 独立に、 水素又は炭素数 1〜 2 0 のへテロ原子及び/又は置換基を有してもよい有機基であり、 Xは 炭素数 2〜 2 0のへテロ原子及び/又は置換基を有してもよい有機 基である。 ） (Wherein, R 2 and R 3 are independently hydrogen or an organic group optionally having 1 to 20 carbon atoms and / or a substituent, and X is 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
で表されるカルボン酸含有ジスルフィ ドのァミン塩化合物。 A carboxylic acid-containing disulfide amine compound represented by the formula:
2. 式 （II) で表わされる 1つの分子にカルボン酸を有するジス ルフィ ド化合物と式 （III) で表わされるァミンとを反応させて式 2. A compound represented by the formula (II) is reacted with a disulfide compound having a carboxylic acid in one molecule and an amine represented by the formula (III).
( I ) で表されるカルボン酸含有ジスルフイ ドのアミン塩化合物を 製造する方法。 A process for producing an amine salt compound of a carboxylic acid-containing disulfide represented by (I).
反応式 （ 1 ) Reaction formula (1)
H00C-X-S-S-X-C00H +
Figure imgf000027_0002
H00C-XSSX-C00H +
Figure imgf000027_0002
(II) (III) ( I ) (II) (III) (I)
(式中、 ， R2 及び R3 は、 独立に、 水素又は炭素数：！〜 2 0 のへテロ原子及び 又は置換基を有してもよい有機基であり、 Xは 炭素数 2〜 2 0のへテロ原子及び 又は置換基を有してもよい有機 基である。 ） (In the formula,, R 2 and R 3 are independently hydrogen or an organic group which may have a hetero atom having 2 to 20 carbon atoms and / or a substituent, and X is 2 to 2 carbon atoms. 0 hetero atom and / or organic group which may have a substituent.
3. 式 （IV) で表わされる 1つの分子にカルボン酸を有するチォ ール化合物と式 （III) で表わされるァミンとを酸化剤の存在下で 反応させて式 （ I ) で表されるカルボン酸含有ジスルフィ ドのアミ ン塩化合物を製造する方法。 3. A carboxylic compound having a carboxylic acid in one molecule represented by the formula (IV) is reacted with an amine represented by the formula (III) in the presence of an oxidizing agent to represent the carboxylic acid represented by the formula (I). A method for producing an amine salt compound of an acid-containing disulfide.
反応式 （2)Reaction formula (2)
Figure imgf000028_0001
Figure imgf000028_0001
(IV) (IV)
(式中、 , R2 及び R3 は、 独立に、 水素又は炭素数 1〜 2 0 のへテロ原子及び 又は置換基を有してもよい有機基であり、 Xは 炭素数 2〜 2 0のへテロ原子及び/又は置換基を有してもよい有機 基である。 ） (In the formula, R 2 and R 3 are each independently hydrogen or an organic group optionally having 1 to 20 carbon atoms and / or a substituent, and X is 2 to 20 carbon atoms. A hetero atom and / or an organic group which may have a substituent.
4. カルボン酸を有するジスルフイ ド化合物 （II) がジチォサリ チル酸である請求項 2に記載のカルボン酸含有ジスルフィ ドのアミ ン塩化合物の製造法。  4. The method for producing an amine salt compound of a carboxylic acid-containing disulfide according to claim 2, wherein the disulfide compound (II) having a carboxylic acid is dithiosalicylic acid.
5. カルボン酸を有するジスルフイ ド化合物 （IV) がジチォジブ ロピオン酸である請求項 3に記載のカルボン酸含有ジスルフイ ドの アミン塩化合物の製造法。  5. The method for producing an amine salt compound of a carboxylic acid-containing disulfide according to claim 3, wherein the disulfide compound (IV) having a carboxylic acid is dithiodibroponic acid.
6. 請求項 1に記載のカルボン酸含有ジスルフイ ドのァミン塩化 合物を含むゴム加硫用配合剤。  6. A rubber vulcanizing compound comprising the carboxylic acid-containing disulfide ammine chloride according to claim 1.
7. ジェン系ゴム及びハロゲン化ゴムからなる群から選ばれる未 加硫ゴム成分並びに請求項 1に記載のカルボン酸含有ジスルフィ ド のァミン塩化合物を含んで成るゴム組成物。  7. A rubber composition comprising an unvulcanized rubber component selected from the group consisting of a gen-based rubber and a halogenated rubber, and a carboxylic acid-containing disulfide amine salt compound according to claim 1.
8. (A) 天然ゴム及び/又はポリイソプレンゴムを少なく とも 3 0重量部以上含むジェン系ゴム 1 0 0重量部、 8. (A) At least natural rubber and / or polyisoprene rubber Geno rubber containing 30 parts by weight or more 100 parts by weight,
(B) 請求項 1 に記載の式 （ I ) で表されるカルボン酸含有ジス ルフイ ドのアミン塩化合物 0. 1〜 5重量部、  (B) 0.1-5 parts by weight of an amine salt compound of a carboxylic acid-containing disulfide represented by the formula (I) according to claim 1;
( C ) よう素吸着量が 7 0〜 ： L 4 0 ( g /kg) 、 D B P吸収量が 6 0〜 1 8 0 ( 1 0 "5 m3 /kg) のカーボンブラック 2 0〜 8 0重 量部並びに (C) Iodine adsorption amount 7 0~: L 4 0 (g / kg), DBP absorption amount 6 0~ 1 8 0 (1 0 "5 m 3 / kg) Carbon black 2 0-8 0 fold Quantity part and
(D) 有機金属塩を金属含有量として 0. 0 5〜 0. 5重量部 を含んでなるタイヤ用ゴム組成物。  (D) A rubber composition for tires comprising 0.05 to 0.5 parts by weight of an organic metal salt as a metal content.
9. 請求項 8に記載のゴム組成物をベルトコート用ゴム及びノ又 はベルトエッジクッショ ンに用いた空気入りタイヤ。  9. A pneumatic tire in which the rubber composition according to claim 8 is used for a rubber for a belt coat and a belt or an edge cushion.
PCT/JP2006/317590 2006-08-14 2006-08-30 Compound of carboxylated disulfide amine salt, process for producing the same, rubber composition containing the compound, and pneumatic tire making use of the same in belt coating rubber and/or belt edge cushion WO2008020488A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US12/377,492 US7714049B2 (en) 2006-08-14 2007-08-09 Compounding agent for rubber vulcanization containing amine salt compound of carboxylic group-containing disulfide, method for producing the same, rubber composition containing the same and pneumatic tire using the same as rubber for belt coat and/or belt edge cush
EP07792560.0A EP2053085B1 (en) 2006-08-14 2007-08-09 Rubber composition for a tire
CN2007800304128A CN101506292B (en) 2006-08-14 2007-08-09 Compounding agent for rubber vulcanization containing amine salt compound of carboxylic acid group-containing disulfide, method for producing the same, rubber composition containing the same, and pneu
PCT/JP2007/065927 WO2008020604A1 (en) 2006-08-14 2007-08-09 Compounding agent for rubber vulcanization containing amine salt compound of carboxylic acid group-containing disulfide, method for producing the same, rubber composition containing the same, and pneumatic tire using the same in rubber for belt coat and/or belt edge cushion

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JP2006227129A JP4124794B2 (en) 2006-08-23 2006-08-23 Pneumatic tire
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04264063A (en) * 1990-10-06 1992-09-18 Cassella Ag Aryl sulfide-, aryl sulfoxide-and aryl sulfone-compounds, and preparation thereof
JPH06501566A (en) * 1990-10-06 1994-02-17 ヘキスト・アクチェンゲゼルシャフト Aryl- and aralkyl sulfide- or sulfone compounds as charge control agents
JP2001089440A (en) * 1999-09-06 2001-04-03 Bayer Ag Method for producing polythiopolycarboxylic acid
JP2003292673A (en) * 2002-04-08 2003-10-15 Yokohama Rubber Co Ltd:The Rubber composition and pneumatic tire using the same
JP2006111685A (en) * 2004-10-13 2006-04-27 Yokohama Rubber Co Ltd:The Carbon black and rubber composition containing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04264063A (en) * 1990-10-06 1992-09-18 Cassella Ag Aryl sulfide-, aryl sulfoxide-and aryl sulfone-compounds, and preparation thereof
JPH06501566A (en) * 1990-10-06 1994-02-17 ヘキスト・アクチェンゲゼルシャフト Aryl- and aralkyl sulfide- or sulfone compounds as charge control agents
JP2001089440A (en) * 1999-09-06 2001-04-03 Bayer Ag Method for producing polythiopolycarboxylic acid
JP2003292673A (en) * 2002-04-08 2003-10-15 Yokohama Rubber Co Ltd:The Rubber composition and pneumatic tire using the same
JP2006111685A (en) * 2004-10-13 2006-04-27 Yokohama Rubber Co Ltd:The Carbon black and rubber composition containing the same

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