WO2018012451A1 - Composition d'additif, et composition de caoutchouc - Google Patents

Composition d'additif, et composition de caoutchouc Download PDF

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Publication number
WO2018012451A1
WO2018012451A1 PCT/JP2017/025106 JP2017025106W WO2018012451A1 WO 2018012451 A1 WO2018012451 A1 WO 2018012451A1 JP 2017025106 W JP2017025106 W JP 2017025106W WO 2018012451 A1 WO2018012451 A1 WO 2018012451A1
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group
rubber composition
rubber
composition according
compound
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PCT/JP2017/025106
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Japanese (ja)
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泰生 上北
中野　貞之
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住友化学株式会社
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention provides an additive composition capable of reducing the loss factor (tan ⁇ ) of a vulcanized rubber composition and suppressing an increase in the viscosity of the rubber composition, and the components of the additive composition, the rubber component, etc.
  • the present invention relates to a rubber composition obtained by kneading.
  • the olefinic double bond reacts with the olefinic double bond of the rubber component, and the amino group is carbon black. It reacts with a carboxy group present on the surface to bond a rubber component and carbon black.
  • the present invention is not limited to such an estimation mechanism.
  • a compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black, such as compound (D), is described above.
  • the loss coefficient of the vulcanized rubber composition can be reduced, but the rubber composition containing the compound (C) has a problem that its viscosity increases.
  • the present invention has been made paying attention to such circumstances, and its purpose is to reduce the loss factor of the vulcanized rubber composition and to suppress the increase in the viscosity of the rubber composition. (I.e., an additive composition having a good balance between the effect of reducing the loss factor of the vulcanized rubber composition and the effect of suppressing the increase in viscosity of the rubber composition).
  • the present invention that can achieve the above object is as follows. [1] a compound (C) having a group or structure (A) capable of reacting with an olefinic double bond, and a group or structure (B) capable of reacting or interacting with carbon black; An additive composition comprising a synthetic polymer having a number average molecular weight of 100,000 or less.
  • the group or structure (A) is an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO 3 H or a salt thereof, * -SS - *, * - C ⁇ N + -O -, * - C ⁇ N + -N - - *, structure represented by the formula (i), structural formula (ii) or formula, (iii) Structure represented by:
  • R 1 represents a C 2-12 alkanediyl group which may have one or more substituents, a C 3-10 cycloalkanediyl group which may have one or more substituents, or one or more substituents.
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, one or more C 1-6 alkoxy group which may have one or more substituents, or one or more substituents.
  • R 4 is a hydroxy group, a C 1-6 alkoxy group which may have one or more substituents, a C 6-14 aryloxy group which may have one or more substituents, or —NR 5.
  • R 6 (wherein R 5 and R 6 each independently represents a hydrogen atom or a C 1-6 alkyl group optionally having one or more substituents).
  • X represents —NH— or —O—.
  • the compound represented by the formula (I) is represented by the formula (II):
  • R 4 is a hydroxy group, a C 1-6 alkoxy group which may have one or more substituents, or a C 6-14 aryloxy group which may have one or more substituents.
  • a solvent of the salt of the compound represented by the formula (I), wherein at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof The additive composition according to any one of [5] to [16], which is a Japanese product.
  • a carboxylate salt of the compound represented by formula (I), wherein at least one selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt thereof The additive composition according to any one of [5] to [16], which is a solvate of
  • the amount of the liquid isoprene rubber modified with at least one selected from the group consisting of carboxylic acid and carboxylic acid anhydride is 50 to 800 parts by weight with respect to 100 parts by weight of the compound (C) [30] ] Additive composition according to any one of [35]. [37] The amount of the liquid isoprene rubber modified with at least one selected from the group consisting of carboxylic acid and carboxylic acid anhydride is 100 to 400 parts by weight with respect to 100 parts by weight of the compound (C). 30]-[35] The additive composition according to any one of [35].
  • the group or structure (A) is an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO 3 H or a salt thereof, * -SS - *, * - C ⁇ N + -O -, * - C ⁇ N + -N - - *, structure represented by the formula (i), the structure represented by formula (ii) or the formula,
  • the compound (C) is at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof.
  • the rubber composition as described.
  • R 4 is a hydroxy group, a C 1-6 alkoxy group which may have one or more substituents, or a C 6-14 aryloxy group which may have one or more substituents.
  • [54] The rubber composition according to any one of [45] to [52], wherein R 4 is a hydroxy group or a C 1-6 alkoxy group.
  • [55] The rubber composition according to any one of [45] to [52], wherein R 4 is a hydroxy group.
  • a solvent of the salt of the compound represented by the formula (I), wherein at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof The rubber composition according to any one of [45] to [56], which is a Japanese product.
  • a carboxylate salt of the compound represented by the formula (I), wherein at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof The rubber composition according to any one of [45] to [56], which is a solvate of
  • the amount of the compound (C) is 0.05 to 20 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
  • the amount of the compound (C) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
  • the amount of the compound (C) is 0.3 to 8 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
  • the amount of the liquid isoprene rubber modified with at least one selected from the group consisting of carboxylic acid and carboxylic acid anhydride is 50 to 800 parts by weight with respect to 100 parts by weight of compound (C).
  • the amount of the liquid isoprene rubber modified with at least one selected from the group consisting of carboxylic acid and carboxylic acid anhydride is 100 to 400 parts by weight with respect to 100 parts by weight of compound (C).
  • the rubber composition according to any one of [41] to [83], wherein the rubber component having an olefinic double bond includes a diene rubber.
  • the rubber composition according to [84], wherein the amount of the diene rubber in the rubber component having an olefinic double bond is 50% by weight or more.
  • the rubber composition according to [84], wherein the amount of the diene rubber in the rubber component having an olefinic double bond is 70 to 100% by weight.
  • the rubber composition according to the above [84], wherein the amount of the diene rubber in the rubber component having an olefinic double bond is 80 to 100% by weight.
  • a method for producing a vulcanized rubber composition comprising vulcanizing the rubber composition obtained by the method according to [94].
  • the loss factor of the vulcanized rubber composition can be reduced and the increase in the viscosity of the rubber composition can be suppressed. it can.
  • the present invention is characterized by using a compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black. I will. Only 1 type may be used for a compound (C) and it may use 2 or more types together.
  • Examples of the group or structure (A) include a group or structure capable of undergoing radical reaction or 1,3-dipole addition reaction with an olefinic double bond. More specifically, examples of the group or structure (A) include an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO 3 H or a salt thereof.
  • any of the amide group, maleimide ring, 1H-imidazole ring, benzoxazole ring, and benzothiazole ring described above may be a monovalent group or a divalent group.
  • Examples of the amide group include * —CO—NH 2 — *, * —NHCO— *, * —CONH 2 (in the above formula, * represents a bonding position).
  • Examples of the maleimide ring include a 1-maleimidyl group.
  • Examples of the 1H-imidazole ring include a 1-imidazolyl group.
  • Examples of the benzoxazole ring include a benzoxazolyl group.
  • Examples of the benzothiazole ring include a benzothiazolyl group.
  • Examples of the group or structure (B) include an unsubstituted or monosubstituted amino group (preferably an unsubstituted amino group), a benzene ring, a furan ring, an oxazole ring, or a 1H-benzimidazole ring.
  • Any of the benzene ring, furan ring, oxazole ring and 1H-benzimidazole ring described above may be a monovalent group or a divalent group.
  • Examples of the benzene ring include a phenyl group and a 1,4-phenylene group.
  • Examples of the furan ring include 2-furyl group and 3-furyl group.
  • Examples of the oxazole ring include a 2-oxazolyl group.
  • Examples of the 1H-benzimidazole ring include a 2-benzimidazolyl group. These can react with the carboxy group of carbon black, or can interact with the aromatic ring of carbon black by ⁇ - ⁇ .
  • the compound (C) include the following compounds. However, the present invention is not limited to these compounds [In the following formula, A represents O, S or NH, m represents an integer of 1 to 6, n represents an integer of 1 to 6, and x represents 1 to Represents an integer of 4].
  • Compound (C) is preferably the formula (I):
  • R 1 in the formula (I) is a C 2-12 alkanediyl group optionally having one or more substituents, and a C 3-10 cycloalkanediyl group optionally having one or more substituents. It represents a divalent C 6-12 aromatic hydrocarbon group which may have one or more substituents, or a combination thereof.
  • C xy means that the number of carbon atoms is x or more and y or less (x, y: integer).
  • the alkanediyl group includes both a linear alkanediyl group and a branched alkanediyl group.
  • examples of the “C 2-12 alkanediyl group” include an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1-methyltrimethylene group, 2-methyl group.
  • Trimethylene 1-ethyltrimethylene, 2-ethyltrimethylene, 1-propyltrimethylene, 2-propyltrimethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltetra Methylene group, 2-ethyltetramethylene group, 1-propyltetramethylene group, 2-propyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethylpentamethylene group Group, 2-ethylpentamethylene group, 3-ethylpentamethylene group, 1-propyl Rupentamethylene group, 2-propylpentamethylene group, 3-propylpentamethylene group, 1-methylhexamethylene group, 2-methylhexamethylene group, 3-methylhexamethylene group, 1-ethylhexamethylene group, 2-ethyl Examples include a hexamethylene group, a 3-ethylhexamethylene group, a 1-
  • Examples of the substituent that the C 2-12 alkanediyl group may have include, for example, a halogen atom, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, a C 1 1- 7 acyl-oxy group, C 6-14 aryl group optionally having one or more substituents.
  • a halogen atom etc. is mentioned later.
  • examples of the “C 3-10 cycloalkanediyl group” include cyclopropane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,5-diyl group, and cyclodecane-1,6-diyl group.
  • the C 3-10 cycloalkanediyl group may have, for example, a halogen atom, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, C 1 A -7 acyl group, a C 1-7 acyl-oxy group, and a C 6-14 aryl group optionally having one or more substituents.
  • examples of the “divalent C 6-12 aromatic hydrocarbon group” include a phenylene group (eg, 1,4-phenylene group), a naphthylene group (eg, 1,4-naphthylene group, 1 , 5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group) and biphenyldiyl group (eg, 1,1′-biphenyl-4,4′-diyl group).
  • a phenylene group eg, 1,4-phenylene group
  • a naphthylene group eg, 1,4-naphthylene group, 1 , 5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group
  • biphenyldiyl group eg, 1,1′-biphenyl-4,4′-diyl group
  • Examples of the substituent that the divalent C 6-12 aromatic hydrocarbon group may have include a halogen atom, a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 alkoxy-carbonyl group.
  • the sulfo group is a group represented by —SO 3 H.
  • R 1 is preferably a C 2-12 alkanediyl group or a divalent C 6-12 aromatic hydrocarbon group, more preferably a C 2-12 alkanediyl group or a phenylene group, still more preferably a phenylene group. Particularly preferred is a 1,4-phenylene group.
  • R 2 and R 3 in formula (I) are each independently a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted C 1-6 alkoxy group, or one or more substituents.
  • halogen atom examples include fluorine, chlorine, bromine and iodine.
  • the alkoxy group includes both a linear alkoxy group and a branched alkoxy group.
  • examples of the “C 1-6 alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group. And hexyloxy group.
  • Examples of the substituent that the C 1-6 alkoxy group may have include, for example, a halogen atom, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, and a C 1-7.
  • An acyl-oxy group, and a C 6-14 aryl group which may have one or more substituents.
  • the alkyl group includes both a linear alkyl group and a branched alkyl group.
  • examples of the “C 1-6 alkyl group” include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, s-butyl group, t-butyl group, 2 -Methylbutyl group, 2-ethylbutyl group, 3-methylbutyl group, 3-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group.
  • Examples of the substituent that the C 1-6 alkyl group may have include, for example, a halogen atom, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, a C 1-7 An acyl-oxy group, and a C 6-14 aryl group which may have one or more substituents.
  • examples of the “C 6-14 aryl group” include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.
  • Examples of the substituent that the C 6-14 aryl group may have include, for example, a halogen atom, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, and a C 1-7.
  • Examples include an acyl group, a C 1-7 acyl-oxy group, a C 6-14 aryl group, and a sulfo group.
  • examples of the “C 1-7 acyl group” include a formyl group, a C 1-6 alkyl-carbonyl group (eg, acetyl group, pivaloyl group), and a benzoyl group.
  • examples of the “C 1-6 alkoxy group” contained in the C 1-6 alkoxy-carbonyl group and the “C 1-7 acyl group” contained in the C 1-7 acyl-oxy group include, for example, Can be mentioned.
  • Examples of the “C 3-10 cycloalkenediyl group formed by combining R 2 and R 3 together with the carbon atom to which they are bonded” include a cyclopropene-1,2-diyl group, Cyclobutene-1,2-diyl group, cyclopentene-1,2-diyl group, cyclohexene-1,2-diyl group, cycloheptene-1,2-diyl group, cyclooctene-1,2-diyl group, cyclononene-1, Examples thereof include 2-diyl group and cyclodecene-1,2-diyl group.
  • Examples of the substituent that the C 3-10 cycloalkenediyl group may have include a halogen atom, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, and a C 1 A -7 acyl group, a C 1-7 acyl-oxy group, and a C 6-14 aryl group optionally having one or more substituents.
  • R 2 and R 3 are each independently preferably a hydrogen atom or a C 1-6 alkyl group, more preferably a hydrogen atom.
  • examples of the “C 6-14 aryl group” contained in the C 6-14 aryloxy group include those described above.
  • R 4 is preferably a hydroxy group, a C 1-6 alkoxy group optionally having one or more substituents, or a C 6-14 aryloxy group optionally having one or more substituents. More preferably a hydroxy group or a C 1-6 alkoxy group, and still more preferably a hydroxy group.
  • X in the formula (I) represents —NH— or —O—.
  • X is preferably —NH—.
  • Compound (I) is preferably represented by the formula (II):
  • the salt of compound (I) includes (a) an amine salt formed by —NH 2 of compound (I) and another acid, and (b) —NH— of compound (I) when X is —NH—.
  • Examples include amine salts formed by-and other acids, and (c) carboxylates formed by -COOH of compound (I) and other bases when R 4 is a hydroxy group.
  • the other acid that forms the amine salt of (a) and (b) may be either an organic acid or an inorganic acid, and the base that forms the carboxylate salt of (c) is an organic base or an inorganic base. Either is acceptable.
  • the salt of compound (I) is preferably a carboxylate, more preferably at least one selected from the group consisting of an alkali metal carboxylate and an alkaline earth metal carboxylate, and more preferably an alkali carboxylate A metal salt, particularly preferably a sodium carboxylate.
  • the solvent that forms the solvate of compound (I) and the solvate of the salt of compound (I) may be water or an organic solvent (for example, methanol).
  • the solvent forming the solvate is preferably water or methanol, more preferably water.
  • Compound (I) or the like is preferably a solvate of a salt of compound (I), more preferably a solvate of a carboxylate salt of compound (I), and more preferably a carboxylic acid of compound (I).
  • Compound (I) and the like can be produced by the method described in Patent Document 1 or a method according to the method.
  • One feature of the present invention is to use a synthetic polymer having a number average molecular weight of 100,000 or less.
  • a synthetic polymer having a number average molecular weight of 100,000 or less.
  • the number average molecular weight (Mn) of the synthetic polymer is a value measured by gel permeation chromatography (GPC). This Mn is preferably 5,000 to 100,000, more preferably 10,000 to 70,000, still more preferably 15,000 to 50,000, and particularly preferably 29,000 to 50,000.
  • the synthetic polymer is preferably liquid isoprene rubber.
  • liquid isoprene rubber means isoprene rubber that is liquid at room temperature (25 ° C.).
  • the liquid isoprene rubber may be unmodified, for example, may be modified with an acid or the like.
  • the synthetic polymer is more preferably an unmodified liquid isoprene rubber. Only one type of unmodified liquid isoprene rubber may be used, or two or more types may be used in combination.
  • the number average molecular weight of the unmodified liquid isoprene rubber is preferably 10,000 to 70,000, more preferably 30,000 to 60,000.
  • the synthetic polymer is more preferably a liquid isoprene rubber (hereinafter referred to as “acid”) modified with at least one selected from the group consisting of carboxylic acid and carboxylic anhydride. It may be abbreviated as “modified liquid isoprene rubber”). Only one type of acid-modified liquid isoprene rubber may be used, or two or more types may be used in combination. By using the compound (C) and the acid-modified liquid isoprene rubber in combination, the loss factor (tan ⁇ ) of the vulcanized rubber composition can be further reduced.
  • acid liquid isoprene rubber
  • modified liquid isoprene rubber Only one type of acid-modified liquid isoprene rubber may be used, or two or more types may be used in combination.
  • carboxylic acid examples include maleic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, citraconic acid, and fumaric acid.
  • carboxylic acid anhydride examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. At least one selected from the group consisting of carboxylic acid and carboxylic acid anhydride is preferably carboxylic acid anhydride, more preferably maleic anhydride.
  • a carboxy group (—COOH) and an acid anhydride group (that is, a carbonyloxycarbonyl group, —C (O) in one molecule of liquid isoprene rubber modified with at least one selected from the group consisting of carboxylic acid and carboxylic acid anhydride ) —O—C (O) —) is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the synthetic polymer is more preferably liquid isoprene rubber modified with carboxylic anhydride, and particularly preferably liquid isoprene rubber modified with maleic anhydride.
  • Number of acid anhydride groups ie, carbonyloxycarbonyl group, —C (O) —O—C (O) —
  • the average value of is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the additive composition of the present invention may contain other components different from the compound (C) and the synthetic polymer.
  • the total amount of the compound (C) and the synthetic polymer is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, based on the whole additive composition of the present invention.
  • the additive composition of the present invention is more preferably composed of the compound (C) and a synthetic polymer.
  • the amount of the synthetic polymer is preferably 10 to 1,000 parts by weight, more preferably 50 to 800 parts by weight, and still more preferably 80 to 500 parts by weight with respect to 100 parts by weight of the compound (C).
  • the synthetic polymer is an acid-modified liquid isoprene rubber
  • the amount thereof is preferably 50 with respect to 100 parts by weight of the compound (C) from the viewpoint of reducing the viscosity of the rubber composition and the loss factor of the vulcanized rubber composition. It is ⁇ 800 parts by weight, more preferably 100 to 400 parts by weight.
  • the present invention provides a rubber composition obtained by kneading the above-mentioned compound (C), a synthetic polymer, a rubber component having an olefinic double bond, and carbon black, and a method for producing the same.
  • the present invention also provides a rubber composition (hereinafter referred to as “sulfur component”) obtained by kneading the above-mentioned compound (C), a synthetic polymer, a rubber component having an olefinic double bond, carbon black, and a sulfur component. And a manufacturing method thereof.
  • the present invention also provides a vulcanized rubber composition obtained by vulcanizing a rubber composition containing a sulfur component, and a method for producing the same.
  • the above-mentioned compound (C) may react with a rubber component having an olefinic double bond during kneading to form another compound. Moreover, the above-mentioned compound (C) decomposes during kneading, and this decomposition product may react with a rubber component having an olefinic double bond to form another compound.
  • this decomposition product may react with a rubber component having an olefinic double bond to form another compound.
  • the rubber composition of the present invention is obtained by kneading the above-mentioned compound (C), a synthetic polymer, a rubber component having an olefinic double bond, and carbon black. Specified. The same applies to the vulcanized rubber composition.
  • the amount of the compound (C) is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and still more preferably 0.1 to 100 parts by weight of the rubber component having an olefinic double bond. 3 to 8 parts by weight.
  • the amount of the synthetic polymer is preferably 10 to 1,000 parts by weight, more preferably 50 to 800 parts by weight, and still more preferably 80 to 500 parts by weight with respect to 100 parts by weight of the compound (C).
  • the synthetic polymer is an acid-modified liquid isoprene rubber
  • the amount thereof is preferably 50 with respect to 100 parts by weight of the compound (C) from the viewpoint of reducing the viscosity of the rubber composition and the loss factor of the vulcanized rubber composition. It is ⁇ 800 parts by weight, more preferably 100 to 400 parts by weight.
  • Examples of rubber components having an olefinic double bond include natural rubber (NR) and modified natural rubber (eg, epoxidized natural rubber, deproteinized natural rubber); styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR). And various synthetic rubbers such as acrylonitrile / butadiene copolymer rubber (NBR) and ethylene / propylene / diene copolymer rubber (EPDM). Only 1 type may be used for the rubber component which has an olefinic double bond, and 2 or more types may be used together.
  • NR natural rubber
  • modified natural rubber eg, epoxidized natural rubber, deproteinized natural rubber
  • SBR styrene-butadiene copolymer rubber
  • BR polybutadiene rubber
  • EPDM ethylene / propylene / diene copolymer rubber
  • the rubber component having an olefinic double bond preferably contains a diene rubber.
  • the diene rubber means a rubber made from a diene monomer having a conjugated double bond.
  • the diene rubber include natural rubber, modified natural rubber, chloroprene rubber, styrene / butadiene copolymer rubber, polybutadiene rubber, and nitrile rubber.
  • the diene rubber is preferably highly unsaturated, and more preferably natural rubber. It is also effective to use natural rubber in combination with another rubber (for example, styrene / butadiene copolymer rubber or polybutadiene rubber).
  • the amount of the diene rubber in the rubber component having an olefinic double bond is preferably 50% by weight or more, more preferably 70 to 100% by weight, even more preferably. Is 80 to 100% by weight.
  • Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, and SIR20.
  • examples of the epoxidized natural rubber include those having a degree of epoxidation of 10 to 60 mol% (for example, ENR25 and ENR50 manufactured by Kumphuran Gasley).
  • As the deproteinized natural rubber a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable.
  • Other modified natural rubbers include, for example, polar groups obtained by reacting natural rubber with 4-vinylpyridine, N, N-dialkylaminoethyl acrylate (for example, N, N-diethylaminoethyl acrylate), 2-hydroxy acrylate, etc. Modified natural rubber.
  • SBR examples include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Among these, solution polymerization SBR is preferable for the rubber composition for treads.
  • the solution polymerization SBR examples include a modified solution polymerization SBR obtained by modification with a modifying agent and having at least one element of nitrogen, tin and silicon at the molecular end.
  • the modifier include lactam compounds, amide compounds, urea compounds, N, N-dialkylacrylamide compounds, isocyanate compounds, imide compounds, silane compounds having an alkoxy group, aminosilane compounds, tin compounds and silane compounds having an alkoxy group.
  • a combined modifier of an alkyl acrylamide compound and a silane compound having an alkoxy group may be used alone or in combination.
  • modified solution polymerization SBR examples include solution polymerization SBR and JSR in which molecular ends are modified using 4,4′-bis (dialkylamino) benzophenone such as “Nipol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd.
  • solutions polymerization SBR in which molecular ends are modified using a tin halide compound such as “SL574” manufactured by the company, and silane-modified solution polymerization SBR such as “E10” and “E15” manufactured by Asahi Kasei.
  • oil-extended SBR in which oil such as process oil or aroma oil is added to emulsion polymerization SBR and solution polymerization SBR is also preferable for the rubber composition for tread.
  • the BR may be either a solution polymerization BR having a low vinyl content or a solution polymerization BR having a high vinyl content, but a solution polymerization BR having a high vinyl content is preferred.
  • a modified solution polymerization BR having at least one element of nitrogen, tin, or silicon at the molecular end obtained by modification with a modifier is particularly preferred.
  • the modifier include 4,4′-bis (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, N-dialkylacrylamide compound, isocyanate compound, imide compound, and alkoxy group.
  • Examples thereof include a silane compound having an alkoxy group (for example, a trialkoxysilane compound), an aminosilane compound, a tin compound and a silane compound having an alkoxy group, and a combined modifier having an alkylacrylamide compound and an silane compound having an alkoxy group. These modifiers may be used alone or in combination.
  • Examples of the modified solution polymerization BR include tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon.
  • BR can be preferably used for a rubber composition for a tread and a rubber composition for a sidewall.
  • BR may be used in a blend with SBR and / or natural rubber (NR).
  • NR natural rubber
  • the amount of SBR and / or NR is 60 to 100% by weight, and the amount of BR is 0 to 40% by weight.
  • the amount of SBR and / or NR is 10 to 70% by weight, and the amount of BR is 90 to 30% by weight. More preferably, the amount of NR is 40 to 60% by weight and the amount of BR is 60 to 40% by weight.
  • a blend of modified SBR and non-modified SBR, a blend of modified BR and non-modified BR, and the like can be preferably used.
  • the rubber component having an olefinic double bond uses SBR, which is excellent in wear resistance and hysteresis loss reduction performance, as a base material.
  • SBR wear resistance and hysteresis loss reduction performance
  • a higher strength NR is optionally used as a base material together with SBR, and it is possible to blend these base materials with BR as necessary to obtain a tread having excellent wear resistance, fatigue resistance, and rebound resilience. Since it is obtained, it is preferable.
  • NR and SBR are blended for passenger car tires, or NR and BR are blended, and NR and BR are blended for truck and bus tires. It is preferable to be used because bending resistance and crack growth resistance are obtained.
  • the rubber composition When the rubber composition is used as an inner liner of a tire, it is difficult to use a blend of IIR and SBR and NR or a blend of IIR and NR as a rubber component having an olefinic double bond. It is preferable because permeability and bending resistance can be obtained.
  • Examples of the carbon black include those described on page 494 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Carbon black may use only 1 type and may use 2 or more types together.
  • HAF High Ablation Furnace
  • SAF Super Abrasion Furnace
  • ISAF Intermediate SAF
  • ISAF-HM Intermediate SAF-HighFurgence
  • FEF FastEurFastGurP
  • SRF Semi-Reinforcing Furnace
  • the amount of carbon black is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, and further preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
  • the sulfur component examples include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, morpholine disulfide, and tetramethylthiuram disulfide.
  • powdered sulfur is preferable, and insoluble sulfur is preferable when the rubber composition is used for manufacturing a tire member having a large amount of sulfur such as a belt member.
  • the amount of the sulfur component is preferably 0.01-30 parts by weight, more preferably 0.1-20 parts by weight, still more preferably 0.1-0.1 parts by weight, relative to 100 parts by weight of the rubber component having an olefinic double bond. 10 parts by weight.
  • the compound (C) in addition to the compound (C), synthetic polymer, rubber component having an olefinic double bond, carbon black, and sulfur component, other components known in the rubber field may be used.
  • Other components include, for example, fillers other than carbon black, compounds capable of binding to silica, vulcanization accelerators, vulcanization accelerators, resins, viscoelasticity improvers, anti-aging agents, oils, waxes, and crackers.
  • all may use only 1 type and may use 2 or more types together.
  • fillers other than carbon black examples include silica (for example, hydrous silica), aluminum hydroxide, bituminous coal pulverized material, talc, clay (particularly, calcined clay), and titanium oxide.
  • silica examples include silica having a CTAB specific surface area of 50 to 180 m 2 / g and silica having a nitrogen adsorption specific surface area of 50 to 300 m 2 / g.
  • examples of commercially available products of silica include “Nipsil (registered trademark) AQ” and “Nipsil (registered trademark) AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultrasil (registered trademark) VN3” and “Ultrasil” manufactured by Degussa.
  • silica having a pH of 6 to 8, (ii) silica containing 0.2 to 1.5% by weight of sodium, (iii) true spherical silica having a roundness of 1 to 1.3, (iv) ) Silicone oil (eg, dimethyl silicone oil), organosilicon compound containing ethoxysilyl group, silica surface-treated with alcohol (eg, ethanol, polyethylene glycol), etc. (v) two or more different nitrogen adsorption specific surface areas Mixtures of silica with can be used as fillers.
  • silicone oil eg, dimethyl silicone oil
  • organosilicon compound containing ethoxysilyl group silica surface-treated with alcohol (eg, ethanol, polyethylene glycol), etc.
  • two or more different nitrogen adsorption specific surface areas Mixtures of silica with can be used as fillers.
  • the amount of silica is preferably in the range of 10 to 120 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
  • the silica / carbon black weight ratio is preferably 0.7 / 1 to 1 / 0.1.
  • aluminum hydroxide examples include aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m 2 / g and a DOP oil supply amount of 50 to 100 ml / 100 g.
  • the average particle size of the bituminous coal pulverized product is usually 0.1 mm or less, preferably 0.05 mm or less, more preferably 0.01 mm or less. Even if a bituminous coal pulverized product having an average particle size exceeding 0.1 mm is used, the hysteresis loss of the rubber composition may not be sufficiently reduced, and the fuel efficiency may not be sufficiently improved. Further, when the rubber composition is used as an inner liner composition, the air permeation resistance of the composition may not be sufficiently improved even when a bituminous coal pulverized product having an average particle size exceeding 0.1 mm is used. is there.
  • the lower limit of the average particle diameter of the bituminous coal pulverized product is not particularly limited, but is preferably 0.001 mm or more. If it is less than 0.001 mm, the cost tends to increase.
  • the average particle size of the bituminous coal pulverized product is a mass-based average particle size calculated from a particle size distribution measured according to JIS Z 8815-1994.
  • the specific gravity of the bituminous coal pulverized product is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. When a bituminous coal pulverized product having a specific gravity exceeding 1.6 is used, the specific gravity of the entire rubber composition increases, and there is a possibility that the fuel efficiency of the tire cannot be sufficiently improved.
  • the specific gravity of the pulverized bituminous coal is preferably 0.5 or more, and more preferably 1.0 or more. If a bituminous coal pulverized product having a specific gravity of less than 0.5 is used, workability during kneading may be deteriorated.
  • the amount is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 70 parts by weight or less, preferably 100 parts by weight of the rubber component having an olefinic double bond. Is 60 parts by weight or less. If this amount is less than 5 parts by weight, the effect of the pulverized bituminous coal may not be sufficiently obtained, and if it exceeds 70 parts by weight, the workability during kneading may be deteriorated.
  • silica When silica is used as the filler, it is preferable to use a compound capable of binding to silica such as a silane coupling agent.
  • the compound include bis (3-triethoxysilylpropyl) tetrasulfide (eg, “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg, “Si— 75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, 3-octanoylthiopropyltriethoxysilane (also known as” octanethioic acid S- [3- ( Triethoxysilyl) propyl] ester ", for example," NXT silane "manufactured by General Electronic Silicons), octanethioic acid S- [3- ⁇ (2-methyl-1,
  • bis (3-triethoxysilylpropyl) tetrasulfide eg “Si-69” manufactured by Degussa
  • bis (3-triethoxysilylpropyl) disulfide eg “Si-75” manufactured by Degussa
  • 3-octanoylthiopropyltriethoxysilane for example, “NXT silane” manufactured by General Electronic Silicons
  • the addition timing of the compound capable of binding to silica is not particularly limited, but it is preferably blended with a rubber component having an olefinic double bond at the same time as silica.
  • the amount of the compound capable of binding to silica is preferably 2 to 10 parts by weight, more preferably 7 to 9 parts by weight with respect to 100 parts by weight of silica.
  • the blending temperature is preferably 80 to 200 ° C, more preferably 110 to 180 ° C.
  • silica when silica is used as a filler, in addition to compounds capable of binding to silica, monohydric alcohols such as ethanol, butanol and octanol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, poly It is also preferable to use polyhydric alcohols such as ether polyols; N-alkylamines; amino acids; liquid polybutadienes whose molecular ends are carboxy-modified or amine-modified.
  • monohydric alcohols such as ethanol, butanol and octanol
  • ethylene glycol diethylene glycol, triethylene glycol
  • polyethylene glycol, polypropylene glycol, pentaerythritol polypropylene glycol
  • polyhydric alcohols such as ether polyols; N-alkylamines; amino acids; liquid polybutadienes whose molecular ends are carb
  • vulcanization accelerators include thiazole-based vulcanization accelerators described in pages 412 to 413 of Rubber Industry Handbook ⁇ Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994), Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators.
  • vulcanization accelerator examples include N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), and N, N-dicyclohexene.
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • BSS N-tert-butyl-2-benzothiazolylsulfenamide
  • N N-dicyclohexene
  • DCBS 2-mercaptobenzothiazole
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfenamide BVS
  • vulcanization accelerators N-cyclohexyl-2-benzothiazolylsulfenamide
  • DCBS N-dicyclohexyl-2-benzothiazolylsulfenamide
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfene vulcanization accelerators
  • BBS amide
  • DCBS N-dicyclohexyl-2-benzothiazolylsulfenamide
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • the ratio of the sulfur component to the vulcanization accelerator is not particularly limited, but the weight ratio of the sulfur component / vulcanization accelerator is preferably 1/10 to 10/1, more preferably 1/5 to 5/1, A preferred range is 1/2 to 2/1.
  • EV vulcanization which is a method of improving heat resistance, in which the ratio of sulfur component / vulcanization accelerator is 1 or less, is preferably used in applications that particularly require improvement in heat resistance. It is done.
  • vulcanization accelerating aid examples include zinc oxide, stearic acid, citraconimide compound, alkylphenol / sulfur chloride condensate, organic thiosulfate compound, and formula (III): R 16 —S—S—R 17 —S—S—R 18 (III) (Wherein R 17 represents a C 2-10 alkanediyl group, and R 16 and R 18 each independently represents a monovalent organic group containing a nitrogen atom.) The compound represented by these is mentioned.
  • zinc oxide is included in the concept of a vulcanization
  • vulcanization acceleration aid zinc oxide, stearic acid, and citraconic imide compounds are preferable, and zinc oxide and stearic acid are more preferable.
  • the amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, still more preferably 100 parts by weight of the rubber component having an olefinic double bond. Is 0.1 to 10 parts by weight.
  • the amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 100 parts by weight of the rubber component having an olefinic double bond. Is 0.1 to 5 parts by weight.
  • biscitraconimides are preferable because they are thermally stable and have excellent dispersibility in a rubber component having an olefinic double bond.
  • citraconic imide compounds a vulcanized rubber composition that is particularly thermally stable, particularly excellent in dispersibility in a rubber component having an olefinic double bond, and having high hardness (Hs) can be obtained (for the reason of (reversion control), 1,3-biscitraconimidomethylbenzene represented by the following formula is preferable.
  • n is an integer of 0 to 10
  • each X is independently an integer of 2 to 4
  • each R 19 is independently a C 5-12 alkyl group.
  • N is preferably an integer of 1 to 9 because the dispersibility of the alkylphenol / sulfur chloride condensate (IV) in the rubber component having an olefinic double bond is good.
  • the alkylphenol-sulfur chloride condensate (IV) tends to become thermally unstable.
  • X is 1, the sulfur content (sulfur in the alkylphenol-sulfur chloride condensate (IV)) Less weight).
  • X is preferably 2 for the reason that high hardness can be expressed efficiently (reversion suppression).
  • R 19 is a C 5-12 alkyl group.
  • R 19 is preferably a C 6-9 alkyl group because the dispersibility of the alkylphenol / sulfur chloride condensate (IV) in the rubber component having an olefinic double bond is good.
  • n 0 to 10
  • X is 2
  • R 19 is an octyl group
  • sulfur content is 24% by weight.
  • the tack roll V200 is mentioned.
  • a vulcanized rubber composition having high hardness (Hs) can be obtained (reversion suppression).
  • Hs hardness
  • k is an integer of 3 to 10.
  • organic thiosulfate compound salt (V) An organic thiosulfate compound salt (V) containing crystal water may be used.
  • the organic thiosulfate compound salt (V) include lithium salt, potassium salt, sodium salt, magnesium salt, calcium salt, barium salt, zinc salt, nickel salt, cobalt salt, etc., potassium salt, sodium salt Is preferred.
  • K is an integer of 3 to 10, preferably an integer of 3 to 6.
  • k is 2 or less, there is a tendency that sufficient heat fatigue resistance cannot be obtained.
  • k is 11 or more, the effect of improving the heat fatigue resistance by the organic thiosulfate compound salt (V) may not be sufficiently obtained.
  • the organic thiosulfate compound salt (V) is preferably a sodium salt monohydrate or a sodium salt dihydrate from the viewpoint of being stable at normal temperature and pressure, and obtained from sodium thiosulfate from the viewpoint of cost.
  • the organic thiosulfate compound salt (V) is more preferable, and sodium 1,6-hexamethylenedithiosulfate dihydrate represented by the following formula is more preferable.
  • R 17 is a C 2-10 alkanediyl group, preferably a C 4-8 alkanediyl group, and more preferably a linear C 4-8 alkanediyl group.
  • R 17 is preferably linear.
  • the carbon number of R 17 is 1 or less, thermal stability may be poor. If the carbon number of R 17 is 11 or more, the distance between the polymers via the vulcanization accelerating aid becomes long, and the effect of adding the vulcanization accelerating aid may not be obtained.
  • R 16 and R 18 are each independently a monovalent organic group containing a nitrogen atom.
  • the monovalent organic group containing a nitrogen atom those containing at least one aromatic ring are preferred, and those containing an aromatic ring and a ⁇ N—C ( ⁇ S) — group (thiocarbamoyl group) are more preferred.
  • R 16 and R 18 may be the same or different, but are preferably the same for reasons such as ease of production.
  • Examples of the compound (III) include 1,2-bis (dibenzylthiocarbamoyldithio) ethane, 1,3-bis (dibenzylthiocarbamoyldithio) propane, 1,4-bis (dibenzylthiocarbamoyldithio) butane 1,5-bis (dibenzylthiocarbamoyldithio) pentane, 1,6-bis (dibenzylthiocarbamoyldithio) hexane, 1,7-bis (dibenzylthiocarbamoyldithio) heptane, 1,8-bis (di Examples include benzylthiocarbamoyldithio) octane, 1,9-bis (dibenzylthiocarbamoyldithio) nonane, 1,10-bis (dibenzylthiocarbamoyldithio)
  • Examples of commercially available products of compound (III) include VULCUREN TRIAL PRODUCT KA9188 and VULCUREN VP KA9188 (1,6-bis (dibenzylthiocarbamoyldithio) hexane) manufactured by Bayer.
  • the rubber composition may contain an organic compound such as resorcinol, a resin such as a resorcinol resin, a modified resorcinol resin, a cresol resin, a modified cresol resin, a phenol resin, and a modified phenol resin.
  • an organic compound such as resorcinol
  • a resin such as a resorcinol resin, a modified resorcinol resin, a cresol resin, a modified cresol resin, a phenol resin, and a modified phenol resin.
  • resorcinol examples include resorcinol manufactured by Sumitomo Chemical Co., Ltd.
  • the resorcinol resin include resorcinol / formaldehyde condensate.
  • modified resorcinol resin examples include those obtained by alkylating a part of the resorcinol resin repeating unit.
  • Penacolite resins B-18-S and B-20 manufactured by India Spec, Sumikanol 620 manufactured by Taoka Chemical Industries, R-6 manufactured by Uniroyal, SRF1501 manufactured by Schenectady Chemical, Ash Examples include Arofine 7209 manufactured by Land.
  • cresol resin examples include a cresol / formaldehyde condensate.
  • modified cresol resin examples include those obtained by modifying the terminal methyl group of the cresol resin to a hydroxy group, and those obtained by alkylating some of the repeating units of the cresol resin. Specifically, Sumikanol 610 manufactured by Taoka Chemical Industry Co., Ltd., PR-X11061 manufactured by Sumitomo Bakelite Co., Ltd., and the like can be given.
  • phenolic resins include phenol / formaldehyde condensates.
  • modified phenolic resins include resins obtained by modifying phenolic resins with cashew oil, tall oil, linseed oil, various animal and vegetable oils, unsaturated fatty acids, rosin, alkylbenzene resins, aniline, melamine, and the like.
  • Examples of other resins include methoxylated methylol melamine resins such as “SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd .; Coumarone resin NG4 (softening point 81-100 ° C.) manufactured by Nippon Steel Chemical Co., Ltd.
  • Coumarone-indene resin such as “Process Resin AC5” (softening point 75 ° C.); Terpene resin such as terpene resin, terpene / phenol resin, and aromatic modified terpene resin; “Nicanol® A70” manufactured by Mitsubishi Gas Chemical Company ”(Softening point 70 to 90 ° C.) and the like; hydrogenated rosin derivatives; novolac alkylphenol resins; resol alkylphenol resins; C5 petroleum resins; liquid polybutadiene.
  • Process Resin AC5 softening point 75 ° C.
  • Terpene resin such as terpene resin, terpene / phenol resin, and aromatic modified terpene resin
  • hydrogenated rosin derivatives novolac alkylphenol resins
  • resol alkylphenol resins C5 petroleum resins
  • Examples of the viscoelasticity improver include N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (for example, “Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), Dithiouracil compounds described in JP-A-63-23942, “Tactrol (registered trademark) AP”, “Tactrol (registered trademark) V-200” manufactured by Taoka Chemical Co., Ltd., alkylphenols described in JP-A-2009-138148, Sulfur chloride condensate, bis (3-triethoxysilylpropyl) tetrasulfide (eg “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg “Si-75” manufactured by Degussa) ), Bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-dieth
  • N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine for example, “Sumifine® 1162” manufactured by Sumitomo Chemical Co., Ltd.
  • bis (3-triethoxysilyl) Propyl) tetrasulfide eg “Si-69” manufactured by Degussa
  • bis (3-triethoxysilylpropyl) disulfide eg “Si-75” manufactured by Degussa
  • 1,6-bis (dibenzylthiocarbamoyl) Dithio) hexane for example, “KA9188” manufactured by Bayer
  • hexamethylene bisthiosulfate disodium salt dihydrate for example, “Parkalink 900” manufactured by Flexis
  • Tecchiroll registered trademark
  • AP Tetrasulfide
  • Anti-aging agents include those described on pages 436 to 443 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association.
  • Anti-aging agents include N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (abbreviation “6PPD”, for example, “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical), reaction of aniline and acetone. Products (abbreviated as “TMDQ”), poly (2,2,4-trimethyl-1,2-) dihydroquinoline) (for example, “Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.), plant A wax is preferably used.
  • the amount thereof is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the rubber component having an olefinic double bond.
  • the amount is preferably 0.1 to 5 parts by weight.
  • Examples of the oil include process oil and vegetable oil.
  • Examples of the process oil include paraffinic process oil, naphthenic process oil, and aromatic process oil.
  • Examples of commercially available products include aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) and process oil (“Diana Process PS32” manufactured by Idemitsu Kosan Co., Ltd.).
  • wax examples include “Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Co., Ltd. and “OZOACE-0355” manufactured by Nippon Seiwa Co., Ltd.
  • the peptizer is not particularly limited as long as it is usually used in the rubber field. For example, it is described in pages 446 to 449 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. And aromatic mercaptan peptizers, aromatic disulfide peptizers, and aromatic mercaptan metal salt peptizers. Of these, dixylyl disulfide and o, o'-dibenzamide diphenyl disulfide ("Noctizer SS" manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) are preferable. Only one type of peptizer may be used, or two or more types may be used in combination.
  • the amount of peptizer is not particularly limited, but is preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the rubber component having an olefinic double bond. Part is more preferred.
  • retarder examples include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) phthalimide (CTP), sulfonamide derivatives, diphenylurea, bis (tridecyl) pentaerythritol diphosphite, and the like.
  • CTP Cyclohexylthio phthalimide
  • the amount of the retarder is not particularly limited, but is preferably 0.01 to 1 part by weight, and 0.05 to 0.5 part by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. More preferred.
  • q is preferably 2 or more, and more preferably 3 or more.
  • q is preferably 16 or less, and more preferably 14 or less. When q is 17 or more, compatibility with a rubber component having an olefinic double bond and reinforcing properties tend to be lowered.
  • the position of the oxyethylene unit in the compound having an oxyethylene unit may be a main chain, a terminal, or a side chain.
  • a compound having oxyethylene units at least in the side chain is preferred from the viewpoint of sustaining the effect of preventing static electricity accumulation on the obtained tire surface and reducing electric resistance.
  • Examples of the compound having an oxyethylene unit in the main chain include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, monoethylene glycol, diethylene glycol, triethylene glycol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene Examples thereof include alkyl ethers, polyoxyethylene alkylamines, polyoxyethylene styrenated alkyl ethers, and polyoxyethylene alkyl amides.
  • the number of oxyethylene units is preferably 4 or more, more preferably 8 or more per 100 carbon atoms constituting the main chain.
  • the electrical resistance tends to increase.
  • the number of oxyethylene units is preferably 12 or less, and more preferably 10 or less.
  • the compatibility with the rubber component having an olefinic double bond and the reinforcing property tend to be lowered.
  • the main chain is preferably composed mainly of polyethylene, polypropylene or polystyrene.
  • the rubber composition of the present invention comprises the above-mentioned compound (C), a synthetic polymer, a rubber component having an olefinic double bond (hereinafter sometimes abbreviated as “rubber component”), carbon black, and others as necessary. It can manufacture by kneading
  • the rubber composition obtained by further kneading the sulfur component is first a step of kneading the rubber component and carbon black or the like (hereinafter sometimes abbreviated as “step 1”), and then a step. It is preferable to produce the rubber composition obtained in 1 through a step of kneading the rubber composition and the sulfur component (hereinafter sometimes abbreviated as “step 2”). Further, a pre-kneading step of kneading the rubber component may be provided before the step 1 (that is, kneading the rubber component with carbon black or the like) to facilitate processing of the rubber component.
  • the total amount of the compound (C) and the synthetic polymer may be kneaded with the rubber component or the like in either the preliminary kneading step, step 1 or step 2,
  • the compound (C) and the synthetic polymer may be divided and kneaded with the rubber component or the like in at least two steps of the preliminary kneading step to step 2.
  • a rubber component or the like When blending zinc oxide, it is preferable to knead with a rubber component or the like in step 1.
  • a vulcanization accelerator When blended, it is preferably kneaded with a rubber component or the like in step 2.
  • a peptizer When blending a peptizer, it is preferable to knead with a rubber component or the like in step 1.
  • knead When providing the preliminary kneading step, it is preferable to knead the entire amount of the peptizer in the preliminary kneading step or to separate the peptizer and knead the rubber component in both the preliminary kneading step and step 1. .
  • an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, an injection molding machine, or the like can be used.
  • the discharge temperature of the rubber composition after kneading in step 1 is preferably 200 ° C. or less, more preferably 120 to 180 ° C.
  • Step 2 For kneading in step 2, for example, an open roll, a calendar, or the like can be used.
  • the kneading temperature in Step 2 (the temperature of the rubber composition being kneaded) is preferably 60 to 120 ° C.
  • a vulcanized rubber composition can be produced by vulcanizing a rubber composition containing the above-described sulfur component. You may manufacture a vulcanized rubber composition by processing the rubber composition containing the above-mentioned sulfur component into a specific shape and then vulcanizing it.
  • the vulcanization temperature is preferably 120 to 180 ° C.
  • a person skilled in the art can appropriately set the vulcanization time according to the composition of the rubber composition. Vulcanization is usually carried out at normal pressure or under pressure.
  • the rubber composition and vulcanized rubber composition of the present invention are useful for producing various products.
  • a vulcanized tire and a tire member are preferable.
  • the tire member include a tire belt member including the vulcanized rubber composition of the present invention and a steel cord, a tire carcass member including the vulcanized rubber composition of the present invention and a carcass fiber cord, and a tire sidewall member. , A tire inner liner member, a tire cap tread member, or a tire under tread member.
  • the vulcanized tire is manufactured by first manufacturing a tire member, combining these to manufacture a raw tire, and vulcanizing the raw tire.
  • the tire manufactured using the rubber composition of the present invention has a low loss factor and can achieve low fuel consumption.
  • the vulcanized rubber composition of the present invention can be used not only for the tire applications described above but also as various anti-vibration rubbers.
  • anti-vibration rubbers include anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers.
  • the anti-vibration rubber can be manufactured by first processing a rubber composition containing a sulfur component into a predetermined shape and then vulcanizing it.
  • Example 1 Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki), 100 parts of natural rubber (RSS # 1), 45 parts of carbon black (N220, ISAF), 3 parts of stearic acid, 5 parts of zinc oxide, anti-aging agent (N -Phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, trade name "Antigen (registered trademark) 6C", manufactured by Sumitomo Chemical Co., Ltd.) 1 part, (2Z) -4-[(4-aminophenyl ) Amino] -4-oxo-2-butenoic acid sodium dihydrate (1 type of compound (C)) and unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd., number average molecular weight: 54,000) 2 parts were kneaded and mixed to obtain a rubber composition.
  • RSS # 1 natural rubber
  • N220 carbon black
  • ISAF carbon black
  • Example 2 A rubber composition and a vulcanized rubber composition in the same manner as in Example 1, except that the blending amount of the unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) in Step 1 was changed from 2 parts to 4 parts. I got a thing.
  • LIR-50 unmodified liquid isoprene rubber
  • Example 3 Instead of 2 parts of unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) in Step 1, 2 parts of unmodified liquid isoprene rubber (“LIR-30” manufactured by Kuraray Co., Ltd., number average molecular weight: 28,000) A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that was added.
  • LIR-50 unmodified liquid isoprene rubber
  • LIR-30 unmodified liquid isoprene rubber
  • Example 4 Instead of 2 parts of unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) in Step 1, maleic anhydride-modified liquid isoprene rubber (“LIR-403” manufactured by Kuraray Co., Ltd.), number average molecular weight: 34,000, Example 1 except that 1 part of the average number of acid anhydride groups in the molecule (ie, carbonyloxycarbonyl group, —C (O) —O—C (O) —): 3) was added. Thus, a rubber composition and a vulcanized rubber composition were obtained.
  • Example 5 Implemented except that 2 parts of maleic anhydride-modified liquid isoprene rubber (Kuraray “LIR-403”) was blended in place of 2 parts of unmodified liquid isoprene rubber (Kuraray "LIR-50”) in Step 1. In the same manner as in Example 1, a rubber composition and a vulcanized rubber composition were obtained.
  • Example 6 Implemented except that 3 parts of maleic anhydride modified liquid isoprene rubber (Kuraray “LIR-403”) was blended in place of 2 parts of unmodified liquid isoprene rubber (Kuraray "LIR-50”) in Step 1. In the same manner as in Example 1, a rubber composition and a vulcanized rubber composition were obtained.
  • Example 7 Implemented except that 4 parts of maleic anhydride modified liquid isoprene rubber (Kuraray “LIR-403”) was blended in place of 2 parts of unmodified liquid isoprene rubber (Kuraray "LIR-50”) in Step 1. In the same manner as in Example 1, a rubber composition and a vulcanized rubber composition were obtained.
  • Example 8 Instead of 2 parts of unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) in Step 1, maleic anhydride modified liquid isoprene rubber (“LIR-410” manufactured by Kuraray Co., Ltd.), number average molecular weight: 30,000 Same as Example 1, except that 2 parts of the average number of acid anhydride groups in the molecule (ie, carbonyloxycarbonyl group, —C (O) —O—C (O) —): 10) was added. Thus, a rubber composition and a vulcanized rubber composition were obtained.
  • LIR-50 unmodified liquid isoprene rubber
  • LIR-410 manufactured by Kuraray Co., Ltd.
  • Example 9 Implemented except that 4 parts of maleic anhydride modified liquid isoprene rubber (Kuraray “LIR-410”) was blended in place of 2 parts of unmodified liquid isoprene rubber (Kuraray “LIR-50”) in Step 1. In the same manner as in Example 1, a rubber composition and a vulcanized rubber composition were obtained.
  • Example 10 In Step 1, 45 parts of carbon black (N330, HAF) is blended instead of 45 parts of carbon black (N220, ISAF), and the amount of unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) is 2 A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that the amount was changed from 4 parts to 4 parts.
  • Example 11 Example 1 except that 4 parts of unmodified liquid isoprene rubber (Kuraray “LIR-30”) was blended in place of 4 parts of unmodified liquid isoprene rubber (Kuraray “LIR-50”) in Step 1. In the same manner as in Example 10, a rubber composition and a vulcanized rubber composition were obtained.
  • Example 12 A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 45 parts of carbon black (N550, FEF) was added instead of 45 parts of carbon black (N220, ISAF) in Step 1. .
  • Example 13 A rubber composition and a vulcanized rubber composition in the same manner as in Example 12 except that the blending amount of unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) was changed from 2 parts to 4 parts in Step 1.
  • LIR-50 unmodified liquid isoprene rubber
  • Comparative Example 1 A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that the unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) was not blended in Step 1.
  • LIR-50 unmodified liquid isoprene rubber
  • Comparative Example 2 A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 10 except that the unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) was not blended in Step 1.
  • LIR-50 unmodified liquid isoprene rubber
  • Comparative Example 3 A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 12 except that the unmodified liquid isoprene rubber (“LIR-50” manufactured by Kuraray Co., Ltd.) was not blended in Step 1.
  • LIR-50 unmodified liquid isoprene rubber
  • Compound Mooney viscosity and viscoelastic properties were measured as follows.
  • Compound Mooney Viscosity The compound Mooney viscosity of the rubber composition was measured at 125 ° C. in accordance with JIS-K6300-1. The smaller the value of the compound Mooney viscosity is, the less rubber scorch occurs and the better the processing stability of the rubber composition.
  • the compound Mooney viscosity of the rubber composition obtained in 11 / the compound Mooney viscosity of the rubber composition obtained in Comparative Example 2 was calculated.
  • Viscoelastic properties The viscoelastic properties (tan ⁇ at 60 ° C.) of the vulcanized rubber composition were measured using a dynamic viscoelasticity measuring device, iplexer 500N, manufactured by GABO. Conditions: temperature 60 ° C., initial strain 10%, dynamic strain 0-2.5%, frequency 10 Hz
  • compound (C) ie, (2Z) -4-[(4-aminophenyl) amino] -4-oxo- is used as an additive for reducing the loss factor of the vulcanized rubber composition.
  • the compound (C) and the synthetic polymer that is, unmodified liquid isoprene rubber or maleic anhydride modified liquid isoprene rubber
  • the compound Mooney viscosity of the rubber composition is reduced.
  • the combined use of the compound (C) and the synthetic polymer can suppress an increase in the viscosity of the rubber composition while maintaining a low loss factor (tan ⁇ ) of the vulcanized rubber composition.
  • the loss coefficient (tan ⁇ ) of the vulcanized rubber composition can be further reduced by using the acid-modified liquid isoprene rubber.
  • the additive composition of the present invention is useful as an additive capable of reducing the loss factor of the vulcanized rubber composition and suppressing the increase in viscosity of the rubber composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit une composition d'additif qui comprend : un composé (C) qui possède un groupe ou une structure (A) permettant une réaction avec une double liaison oléfinique, et un groupe ou une structure (B) permettant une réaction ou une interaction avec un noir de carbone ; et un polymère synthétique de masse moléculaire moyenne en nombre inférieure ou égale à 100000.
PCT/JP2017/025106 2016-07-11 2017-07-10 Composition d'additif, et composition de caoutchouc WO2018012451A1 (fr)

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CN112839968B (zh) * 2018-10-11 2023-10-13 米其林集团总公司 包括增强件元件的橡胶部件

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