WO2008020488A1 - Composé de sel d'amine de disulfure carboxylé, procédé servant à le produire, composition de caoutchouc contenant le composé et pneumatique en faisant usage dans le caoutchouc de revêtement de ceinture et/ou le bandage de rebord de ceinture - Google Patents

Composé de sel d'amine de disulfure carboxylé, procédé servant à le produire, composition de caoutchouc contenant le composé et pneumatique en faisant usage dans le caoutchouc de revêtement de ceinture et/ou le bandage de rebord de ceinture 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
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English (en)
Japanese (ja)
Inventor
Wonmun Choi
Yuuki Shimizu
Original Assignee
The Yokohama Rubber Co., Ltd.
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Filing date
Publication date
Priority claimed from JP2006227129A external-priority patent/JP4124794B2/ja
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 CN2007800304128A priority patent/CN101506292B/zh
Priority to EP07792560.0A priority patent/EP2053085B1/fr
Priority to PCT/JP2007/065927 priority patent/WO2008020604A1/fr
Publication of WO2008020488A1 publication Critical patent/WO2008020488A1/fr

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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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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des composés de sel d'amine de disulfure carboxylé représentés par la formule (I) (dans laquelle chacun de R1, R2 et R3 représente indépendamment un hydrogène ou un groupe organique en C1-C20 ayant éventuellement un hétéroatome et/ou un substituant; et X est un groupe organique en C2-C20 ayant éventuellement un hétéroatome et/ou un substituant). De plus, l'invention concerne un procédé servant à les produire et une composition de caoutchouc contenant l'un quelconque de ceux-ci de façon à parvenir à augmenter la vitesse de vulcanisation et les propriétés du caoutchouc vulcanisé sans affecter négativement le temps de grillage. En outre, l'invention concerne une composition de caoutchouc pour pneumatique comprenant 100 parties en poids d'un caoutchouc diénique (A) contenant au moins 30 parties en poids de caoutchouc naturel et/ou de caoutchouc de polyisoprène; 0,1 à 5 parties en poids de composé de sel d'amine de disulfure carboxylé (B) représenté par la formule (I); 20 à 80 parties en poids de noir de carbone (C) ayant une adsorption de l'iode de 70 à 140 (g/kg) et une absorption de DBP de 60 à 180 (10-5 m3/kg); et 0,05 à 0,5 partie en poids, en termes de teneur en métal, d'un sel organométallique (D) de façon à améliorer les performances d'adhérence à la ceinture en métal et à avoir une faible accumulation de la chaleur. Enfin, l'invention concerne un pneumatique faisant usage de la composition de caoutchouc pour pneumatique dans son caoutchouc de revêtement de ceinture et/ou son bandage de rebord de ceinture.
PCT/JP2006/317590 2006-08-14 2006-08-30 Composé de sel d'amine de disulfure carboxylé, procédé servant à le produire, composition de caoutchouc contenant le composé et pneumatique en faisant usage dans le caoutchouc de revêtement de ceinture et/ou le bandage de rebord de ceinture WO2008020488A1 (fr)

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
CN2007800304128A CN101506292B (zh) 2006-08-14 2007-08-09 包含含羧酸基二硫化物胺盐化合物的橡胶硫化用复合剂，其制备方法，包含它的橡胶组合物和使用它作为带涂层和/或带边缘衬垫用橡胶的充气轮胎
EP07792560.0A EP2053085B1 (fr) 2006-08-14 2007-08-09 Composition de caoutchouc pour pneus
PCT/JP2007/065927 WO2008020604A1 (fr) 2006-08-14 2007-08-09 Agent de formulation pour vulcanisation de caoutchouc contenant un composé de sel aminé de disulfure contenant un groupe d'acide carboxylique, procédé de production de celui-ci, composition de caoutchouc contenant celui-ci et pneu utilisant celui-ci pour le revêtement de ceinture et/ou la gomme d

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-221258 2006-08-14
JP2006221258 2006-08-14
JP2006227129A JP4124794B2 (ja) 2006-08-23 2006-08-23 空気入りタイヤ
JP2006-227129 2006-08-23

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WO2008020488A1 true WO2008020488A1 (fr) 2008-02-21

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PCT/JP2006/317590 WO2008020488A1 (fr) 2006-08-14 2006-08-30 Composé de sel d'amine de disulfure carboxylé, procédé servant à le produire, composition de caoutchouc contenant le composé et pneumatique en faisant usage dans le caoutchouc de revêtement de ceinture et/ou le bandage de rebord de ceinture

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Country Link
WO (1) WO2008020488A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04264063A (ja) * 1990-10-06 1992-09-18 Cassella Ag アリールスルフィド−　、アリールスルホキシド−　及びアリールスルホン化合物並びにその製造方法
JPH06501566A (ja) * 1990-10-06 1994-02-17 ヘキスト・アクチェンゲゼルシャフト 電荷制御剤としてのアリール−およびアルアルキルスルフィッド−またはスルホン化合物
JP2001089440A (ja) * 1999-09-06 2001-04-03 Bayer Ag ポリチオポリカルボン酸の製造方法
JP2003292673A (ja) * 2002-04-08 2003-10-15 Yokohama Rubber Co Ltd:The ゴム組成物およびそれを用いた空気入りタイヤ
JP2006111685A (ja) * 2004-10-13 2006-04-27 Yokohama Rubber Co Ltd:The カーボンブラック及びそれを含むゴム組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04264063A (ja) * 1990-10-06 1992-09-18 Cassella Ag アリールスルフィド−　、アリールスルホキシド−　及びアリールスルホン化合物並びにその製造方法
JPH06501566A (ja) * 1990-10-06 1994-02-17 ヘキスト・アクチェンゲゼルシャフト 電荷制御剤としてのアリール−およびアルアルキルスルフィッド−またはスルホン化合物
JP2001089440A (ja) * 1999-09-06 2001-04-03 Bayer Ag ポリチオポリカルボン酸の製造方法
JP2003292673A (ja) * 2002-04-08 2003-10-15 Yokohama Rubber Co Ltd:The ゴム組成物およびそれを用いた空気入りタイヤ
JP2006111685A (ja) * 2004-10-13 2006-04-27 Yokohama Rubber Co Ltd:The カーボンブラック及びそれを含むゴム組成物

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