WO2014061526A1 - ゴム組成物及びこれを用いる空気入りタイヤ - Google Patents
ゴム組成物及びこれを用いる空気入りタイヤ Download PDFInfo
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- WO2014061526A1 WO2014061526A1 PCT/JP2013/077484 JP2013077484W WO2014061526A1 WO 2014061526 A1 WO2014061526 A1 WO 2014061526A1 JP 2013077484 W JP2013077484 W JP 2013077484W WO 2014061526 A1 WO2014061526 A1 WO 2014061526A1
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- 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
- B60C1/0016—Compositions of the tread
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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
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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
- C08K3/06—Sulfur
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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
- C08K3/08—Metals
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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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
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
Definitions
- the present invention relates to a rubber composition and a pneumatic tire using the same.
- Patent Documents 1 to 3 a composition containing tin can be used in a rubber composition for a tire or the like.
- JP 2011-57946 A International Publication No. 2007-119675 Japanese Patent No. 3913346
- the rubber composition is a divalent tin carboxylate such as bis (2-ethylhexanoate) tin; a tetraalkyltin (having tetravalent tin); a dialkyltin dihalide (tetravalent tin) )
- tetraalkyltin having tetravalent tin
- dialkyltin dihalide tetravalent tin
- the present inventor has moderately promoted the condensation reaction between the silane coupling agent and silica, although the divalent tin compound and the tetravalent tin compound as described above, From the results that the breaking strength, elongation at break, etc. are reduced, these tin compounds have a chemical reaction of sulfur-containing compound-rubber (for example, sulfur-rubber or sulfur-containing vulcanization accelerator-rubber, silica-sulfur-containing silane cup).
- sulfur-containing compound-rubber for example, sulfur-rubber or sulfur-containing vulcanization accelerator-rubber, silica-sulfur-containing silane cup.
- the chemical reaction of the ring agent-rubber the same applies hereinafter
- the chemical reaction of the sulfur-containing compounding agent-rubber was not promoted.
- the present inventor further researched, and by adding a sulfur-containing compounding agent and a tin oxide compound to a sulfur-crosslinkable diene-based rubber, it is included in the chemical reaction of the sulfur-containing compound-rubber, for example, Sulfur-Rubber, Sulfur-containing Vulcanization Accelerator-Rubber, Silica-Sulfur-containing Silane Coupling Agent-Rubber Accelerates chemical reaction in a well-balanced manner, breaking strength (TB), breaking elongation (EB), modulus, low temperature and high temperature
- Sulfur-Rubber Sulfur-containing Vulcanization Accelerator-Rubber
- Silica-Sulfur-containing Silane Coupling Agent-Rubber Accelerates chemical reaction in a well-balanced manner, breaking strength (TB), breaking elongation (EB), modulus, low temperature and high temperature
- breaking strength breaking strength
- EB breaking elongation
- modulus modulus
- the present invention provides the following rubber composition and a pneumatic tire using the same.
- 1. 1 to 100 parts by mass of carbon black and / or 10 to 150 parts by mass of an inorganic filler, 1 to 30 parts by mass of a sulfur-containing compound, and 0.1 to A rubber composition comprising 1 to 20 parts by mass.
- 2. The rubber composition according to 1 above, wherein the tin oxide compound is a compound represented by the following formula (1).
- n is 1 or 2
- R 1 and R 2 each independently have a substituent, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxy group, or 1 to 20 carbon atoms
- An alkoxy group, —NRR ′ group (wherein R and R ′ each independently have a substituent, a hydrocarbon group having 1 to 20 carbon atoms, or hydrogen), halogen or hydrogen . ] 3.
- the sulfur-containing compounding agent is at least one selected from the group consisting of sulfur, a sulfur-containing silane coupling agent, and a sulfur-containing vulcanization accelerator. 4).
- the inorganic filler is silica
- the sulfur-containing compounding agent contains at least a sulfur-containing silane coupling agent
- the amount of the sulfur-containing silane coupling agent is 1 to 15 masses per 100 parts by mass of the diene rubber. 4.
- the rubber composition of the present invention and the pneumatic tire of the present invention are excellent in low heat buildup, wet grip performance, breaking strength, breaking elongation, and modulus without deteriorating workability.
- FIG. 1 is a cross-sectional view schematically showing a partial cross section in a tire meridian direction of an example of an embodiment of a pneumatic tire of the present invention.
- the rubber composition of the present invention comprises 1 to 100 parts by mass of carbon black and / or 10 to 150 parts by mass of an inorganic filler and 1 to 30 parts by mass of a sulfur-containing compounding agent with respect to 100 parts by mass of a sulfur-crosslinkable diene rubber. Part and 0.1 to 20 parts by mass of a tin oxide compound.
- a sulfur-containing compound and a tin oxide compound are compounded with a sulfur-crosslinkable diene rubber to accelerate the chemical reaction of the sulfur-containing compound-rubber in a well-balanced manner, so that TB, EB, modulus, and low temperature
- the high-temperature tan ⁇ balance is highly balanced, and it has become possible to obtain a compound having excellent breaking strength, breaking elongation, low heat build-up, and wet grip performance without degrading workability.
- the diene rubber contained in the rubber composition of the present invention is not particularly limited as long as sulfur crosslinking is possible.
- Specific examples thereof include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), aromatic vinyl-conjugated diene copolymer rubber, acrylonitrile-butadiene copolymer rubber (NBR), and butyl rubber (IIR). ), Halogenated butyl rubber (Br-IIR, Cl-IIR), chloroprene rubber (CR) and the like.
- an aromatic vinyl-conjugated diene copolymer rubber as the diene rubber because a tire excellent in wet grip performance can be obtained.
- the aromatic vinyl-conjugated diene copolymer rubber include styrene-butadiene copolymer rubber (SBR) and styrene-isoprene copolymer rubber.
- SBR styrene-butadiene copolymer rubber
- SBR styrene-butadiene copolymer rubber
- the weight average molecular weight of the diene rubber is preferably 200,000 to 2,500,000 from the viewpoint of excellent workability, low heat build-up, wet grip performance, breaking strength, breaking elongation, and modulus.
- the weight average molecular weight (Mw) of the diene rubber is measured in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
- GPC gel permeation chromatography
- the diene rubber is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
- the diene rubbers can be used alone or in combination of two or more.
- Carbon black that can be blended in the rubber composition of the present invention is not particularly limited. For example, a conventionally well-known thing is mentioned. Carbon blacks can be used alone or in combination of two or more.
- the amount of carbon black is 1 to 100 parts by mass with respect to 100 parts by mass of the sulfur-crosslinkable diene rubber.
- the amount of carbon black is preferably 3 to 90 parts by weight with respect to 100 parts by weight of the diene rubber from the viewpoint of excellent workability, low heat build-up, wet grip performance, breaking strength, breaking elongation, and modulus. It is more preferably 5 to 80 parts by mass.
- the inorganic filler that can be blended in the rubber composition of the present invention is not particularly limited. Examples thereof include silica, calcium carbonate, clay and talc. One preferred embodiment is that the inorganic filler is silica. In the present invention, the inorganic filler excludes the carbon black.
- the silica contained in the rubber composition of the present invention is not particularly limited. Any conventionally known silica compounded in the rubber composition for use in tires or the like can be used. Examples of silica include wet silica, dry silica, fumed silica, diatomaceous earth, and the like. Silica preferably contains wet silica from the viewpoint of rubber reinforcement.
- Silica preferably has a cetyltrimethylammonium bromide (CTAB) adsorption specific surface area of 100 to 300 m 2 / g from the viewpoint of being excellent in low exothermic property, workability, wet grip performance, breaking strength, breaking elongation, and modulus. More preferably, it is 140 to 200 m 2 / g.
- CTAB adsorption specific surface area is a surrogate property of the surface area that silica can use for adsorption with the silane coupling agent, and the amount of CTAB adsorption on the silica surface is JIS K6217-3: 2001 “Part 3: Specific surface area of This is a value measured according to “How to obtain—CTAB adsorption method”.
- An inorganic filler can be used individually or in combination of 2 types or more, respectively.
- the sulfur-containing compound contains at least a sulfur-containing silane coupling agent from the viewpoint of being excellent in low exothermic property, workability, wet grip performance, breaking strength, breaking elongation, and modulus. It is mentioned as one of the preferable aspects.
- the content of the inorganic filler is 10 to 150 parts by mass with respect to 100 parts by mass of the diene rubber, and is excellent in low exothermic property, workability, wet grip performance, breaking strength, breaking elongation, and modulus.
- the amount is preferably 20 to 120 parts by mass, and more preferably 40 to 100 parts by mass.
- the sulfur-containing compounding agent contained in the present invention is not particularly limited as long as it is a compound having a sulfur atom.
- the sulfur-containing compounding agent can be, for example, at least one selected from the group consisting of sulfur, a sulfur-containing silane coupling agent, and a sulfur-containing vulcanization accelerator.
- the sulfur-containing silane coupling agent is not particularly limited as long as it is a silane coupling agent having a sulfur atom.
- a polysulfide silane coupling agent having a polysulfide bond having three or more sulfur atoms such as bis (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropylbenzothiazole tetrasulfide
- Disulfide-based silane coupling agents such as ethoxysilylpropyl) disulfide
- Thiocarboxylate-based silane coupling agents such as 3-octanoylthiopropyltriethoxys
- a polysulfide-based silane coupling agent in which a sulfur atom has two or more polysulfide bonds is preferable from the viewpoint of low exothermic property, workability, wet grip performance, breaking strength, breaking elongation, and modulus.
- a polysulfide silane coupling agent having 2 to 5 polysulfide bonds is more preferable, and bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide are more preferable.
- the present inventor when using silica, a sulfur-containing silane coupling agent and a tin oxide compound, which will be described later, with respect to a diene rubber, the low heat build-up, workability, wet grip performance, breaking strength, breaking elongation, modulus From the viewpoint of superiority, it has been found that a polysulfide-based silane coupling agent in which a sulfur atom has two or more polysulfide bonds is preferable.
- a sulfide bond having two or more sulfur atoms is represented by-(S) x- (X: 2 or more).
- a polysulfide bond is a bond having two and / or more sulfur atoms between two carbon atoms.
- the tin oxide compound moderately suppresses the deactivation of the tin oxide compound due to desulfurization of the sulfur atom from the polysulfide silane coupling agent having 3 or more sulfur atoms
- the sulfur-containing compound-rubber Accelerates chemical reactions (for example, sulfur-rubber, sulfur-containing vulcanization accelerator-rubber, silica-sulfur-containing silane coupling agent-rubber chemical reaction), which results in better, lower heat build-up, processability
- the inventors of the present application infer that it contributes to wet grip performance, breaking strength, breaking elongation, and modulus.
- silica-sulfur-containing silane coupling agent-rubber the chemical reaction of silica-sulfur-containing silane coupling agent-rubber is particularly promoted. Specifically, silica-sulfur-containing silane coupling agent condensation reaction, sulfur-containing silane coupling agent-rubber crosslinking reaction At the same time is thought to promote well-balanced.
- the sulfur-containing vulcanization accelerator is not particularly limited as long as it is a vulcanization accelerator that has a sulfur atom and can be used in the rubber composition.
- the sulfur-containing vulcanization accelerator includes a sulfur-containing vulcanization acceleration aid.
- the sulfur-containing vulcanization accelerator include thiuram compounds such as tetramethylthiuram disulfide and tetramethylthiuram monosulfide; dithiocarbamates such as zinc dimethyldithiocarbamate; 2-mercaptobenzothiazole and dibenzothiazyl disulfide.
- Examples thereof include thiazole compounds such as N-cyclohexyl-2-benzothiazole sulfenamide and sulfenamide compounds such as Nt-butyl-2-benzothiazole sulfenamide.
- thiazole compounds such as N-cyclohexyl-2-benzothiazole sulfenamide
- sulfenamide compounds such as Nt-butyl-2-benzothiazole sulfenamide.
- N-cyclohexyl-2-benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothia is preferred from the viewpoint of excellent workability, low heat build-up, wet grip performance, breaking strength, breaking elongation, and modulus.
- Zolylsulfenamide is preferred.
- the sulfur-containing compounding agents can be used alone or in combination of two or more.
- the amount of the sulfur-containing compounding agent is 1 to 30 parts by mass with respect to 100 parts by mass of the diene rubber. From the viewpoint of superior workability, low heat build-up, wet grip performance, breaking strength, breaking elongation, and modulus, the amount of the sulfur-containing compounding agent is 1.5 to 25 parts by mass with respect to 100 parts by mass of the diene rubber. It is preferably 2 to 20 parts by mass.
- the amount of sulfur is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
- the amount of the sulfur-containing vulcanization accelerator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
- the amount of the sulfur-containing silane coupling agent is 1 to 15 parts by mass with respect to 100 parts by mass of the diene rubber from the viewpoint of excellent workability, low heat build-up, wet grip performance, breaking strength, breaking elongation, and modulus. It is preferably 3 to 12 parts by mass.
- the tin oxide compound contained in the rubber composition of the present invention is not particularly limited as long as it is a compound having a Sn ⁇ O bond.
- the tin oxide compound can have an organic group.
- One preferred embodiment is that the organic group is bonded to a tin atom.
- the organic group include hydrocarbon groups that can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
- the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof, which may be linear or branched and have an unsaturated bond. May be.
- an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an —NRR ′ group (wherein R and R ′ are each independently A hydrocarbon group having 1 to 20 carbon atoms and / or hydrogen).
- the substituent include a hydroxy group, a carboxyl group, a cyano group, an amino group, and a halogen.
- the tin oxide compound has a functional group such as a hydroxy group (—OH group), an amino group (—NH 2 group), or a halogen (eg, —F, —Cl, —Br, —I) on the tin atom.
- a hydrogen (—H) group is bonded.
- the tin oxide compound is preferably a compound represented by the following formula (1) from the viewpoint of being excellent in low exothermic property, workability, wet grip performance, breaking strength, breaking elongation, and modulus.
- the compound represented by the formula (1) has a Sn ⁇ O bond.
- n is 1 or 2
- R 1 and R 2 each independently have a substituent, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxy group, or 1 to 20 carbon atoms
- An alkoxy group, —NRR ′ group (wherein R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms or hydrogen), halogen or hydrogen. ]
- Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, an octyl group, a decyl group, and a dodecyl group.
- Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.
- R and R ′ each independently have a substituent, which is a hydrocarbon group having 1 to 20 carbon atoms, or hydrogen, and may have a substituent, 1 carbon atom
- the hydrocarbon groups of ⁇ 20 are the same as above.
- Examples of the —NRR ′ group include a dimethylamino group, a diethylamino group, a dicyclohexyl group, a diphenyl group, and an amino group.
- halogen include -F, -Cl, -Br, and -I.
- the tin oxide compound can include at least the compound represented by the formula (1).
- tin oxide compound examples include di-n-octyl tin oxide represented by the following formula, Mono-n-octyltin oxide, a compound containing mono-n-octyltin oxide represented by the following formula: Is mentioned.
- the amount of the tin oxide compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber, depending on the low heat build-up, workability, wet grip performance, breaking strength, breaking elongation, and modulus. From the viewpoint of superiority, it is preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
- the rubber composition of the present invention can further contain a sulfur-free silane coupling agent.
- an inorganic filler is a silica
- the silane coupling agent not containing sulfur is not particularly limited.
- an aminosilane coupling agent, an epoxysilane coupling agent, and a hydroxysilane coupling agent can be used.
- the amount of the silane coupling agent not containing sulfur is 1 with respect to 100 parts by mass of the diene rubber from the viewpoint of excellent workability, low heat build-up, wet grip performance, breaking strength, breaking elongation, and modulus.
- the amount is preferably ⁇ 15 parts by mass, and more preferably 3 to 12 parts by mass.
- the rubber composition of the present invention may further contain an additive within a range that does not impair its effects and purposes.
- additives include, but are not limited to, zinc oxide, stearic acid, anti-aging agent, processing aid, aroma oil, liquid polymer, terpene resin, thermosetting resin, and sulfur contained in the rubber composition of the present invention.
- Various additives generally used for rubber compositions such as a vulcanizing agent, a vulcanization accelerator having no sulfur atom, and a vulcanization accelerating aid having no sulfur atom, may be mentioned.
- the rubber composition of the present invention is not particularly limited for its production. Specifically, for example, a method of kneading the above-described components using a known method or apparatus (for example, a Banbury mixer, a kneader, a roll, or the like) can be used.
- the rubber composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
- the rubber composition of the present invention can be used, for example, for tires, belts, hoses and the like.
- the pneumatic tire of the present invention is a pneumatic tire using the rubber composition of the present invention for a cap tread.
- the rubber composition used in the present invention is not particularly limited as long as it is the rubber composition of the present invention.
- the cap tread of the pneumatic tire of the present invention is manufactured using the rubber composition of the present invention.
- FIG. 1 is a cross-sectional view schematically showing a partial cross section in the tire meridian direction of an example of an embodiment of a pneumatic tire of the present invention.
- reference numeral 1 is a cap tread
- reference numeral 2 is a sidewall
- reference numeral 3 is a bead.
- FIG. 1 two layers of carcass 4 in which reinforcing cords extending in the tire radial direction are arranged at predetermined intervals in the tire circumferential direction between the left and right beads 3 and embedded in a rubber layer are extended, and both end portions thereof are A bead filler 6 is sandwiched around a bead core 5 embedded in the bead 3 and folded back from the inner side in the tire axial direction.
- An inner liner 7 is disposed inside the carcass 4.
- a two-layer belt 8 is disposed in which reinforcing cords inclined and extending in the tire circumferential direction are arranged at predetermined intervals in the tire axial direction and embedded in a rubber layer. ing.
- the reinforcing cords of the two-layer belt 8 cross each other with the inclination directions with respect to the tire circumferential direction being opposite to each other.
- a belt cover 9 is disposed on the outer peripheral side of the belt 8.
- a cap tread 1 is formed by a cap tread rubber layer 12 on the outer peripheral side of the belt cover 9.
- a side rubber layer 13 is disposed outside the carcass 4 of each sidewall 2, and a rim cushion rubber layer 14 is provided outside the folded portion of the carcass 4 of each bead 3.
- the cap tread 1 is composed of the rubber composition of the present invention.
- the pneumatic tire of the present invention is not particularly limited except that the rubber composition of the present invention is used for a pneumatic tire, and can be produced, for example, according to a conventionally known method.
- inert gas such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure, can be used.
- tan ⁇ (0 ° C.) indicates that the larger the index, the better the wet grip performance.
- the tan ⁇ (50 ° C.) indicates that the smaller the index, the lower the exothermic property.
- ⁇ Measurement of tensile stress (modulus), tensile strength (breaking strength, TB), elongation at break (EB) A JIS No. 3 dumbbell-shaped test piece was punched from a vulcanized rubber test piece, and a tensile test at a pulling speed of 500 mm / min was performed according to JIS. The measurement was performed in accordance with K6251 and the vulcanized rubber specimens were measured for 100% modulus, tensile strength, and elongation at break at room temperature.
- -Measurement of screw Based on JIS K6300, the Mooney viscosity ML (1 + 4) 100 degreeC of the unvulcanized rubber composition was calculated
- -Measurement of scorch time Based on JIS K6300, the time (minute) for which the viscosity of an unvulcanized rubber composition rose 5 points
- E-SBR Emulsion polymerization SBR Nipol 1502, manufactured by Nippon Zeon Co., Ltd.
- Di-n-octyltin oxide Compound represented by the following formula, Hokuko Chemical Industries
- DOTO Mono-n-octyltin oxide: a compound containing mono-n-octyltin oxide represented by the following formula, MOTO manufactured by Hokuko Chemical Co., Ltd.
- Tetra-n-octyltin (n-C 8 H 17 ) 4 Sn, TOT manufactured by Hokuko Chemical Co., Ltd.
- Di-n-octyltin dichloride (nC 8 H 17 ) 2 SnCl 2 , Hokuko Chemical Industries DOTC ⁇ Bis (2-ethylhexanoic acid) tin: manufactured by Kishida Chemical Co., Ltd. ⁇ Silica: wet silica, Nippon Silica Co., Ltd. nip seal AQ, CTAB adsorption specific surface area 170 m 2 / g ⁇ Carbon black: Show black N339M manufactured by Showa Cabot ⁇ Zinc oxide: Zinc Hua No. 3 manufactured by Shodo Chemical Co., Ltd.
- Stearic acid Stearic acid manufactured by NOF Corporation
- Anti-aging agent Anti-aging agent (S-13), Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
- -Sulfur-containing silane coupling agent bis (triethoxysilylpropyl) tetrasulfide. It has —S 4 — as the polysulfide. Both ends of —S 4 — are bonded to a carbon atom.
- Sulfur-containing vulcanization accelerator (CZ) N-cyclohexyl-2-benzothiazolylsulfenamide, Sunseller CM-PO manufactured by Sanshin Chemical Co., Ltd.
- Vulcanization accelerator (DPG) Diphenylguanidine, Sunsell DG made by Sanshin Chemical Co., Ltd.
- Comparative Examples 4 and 5 containing di-n-octyltin dichloride as a tin compound other than the tin oxide compound, Mooney vis, tensile strength, and elongation at break decreased, and Comparative Example 4 showed no improvement in modulus.
- Comparative Examples 6 and 7 containing bis (2-ethylhexanoic acid) tin as a tin compound other than the tin oxide compound, Mooney bis, Mooney scorch, modulus, tensile strength, and elongation at break decreased.
- Examples 1 to 4 are excellent in low heat buildup, wet grip performance, breaking strength, breaking elongation, and modulus without degrading workability.
- Comparative Example 10 containing di-n-octyltin dichloride as a tin compound other than the tin oxide compound has a short Mooney scorch, little improvement in tensile strength and modulus, low elongation at break, wet grip, The exotherm decreased.
- Comparative Example 11 containing bis (2-ethylhexanoic acid) tin as a tin compound other than the tin oxide compound the Mooney bis increased, the modulus and the tensile strength were not improved so much, and the elongation at break was lowered.
- Examples 5 and 6 are excellent in low exothermic property, wet grip performance, breaking strength, breaking elongation, and modulus without deteriorating workability.
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Abstract
Description
そこで、本発明は、加工性を悪化させることなく、破壊強度、破断伸び、低発熱性、ウェットグリップ性能に優れるゴム組成物を提供することを目的とする。
1. 硫黄架橋可能なジエン系ゴム100質量部に対して、カーボンブラック1~100質量部及び/又は無機充填材10~150質量部と、含硫黄配合剤1~30質量部と、スズオキサイド化合物0.1~20質量部とを配合してなるゴム組成物。
2. 前記スズオキサイド化合物が、下記式(1)で表わされる化合物である上記1に記載のゴム組成物。
3. 前記含硫黄配合剤が、硫黄、含硫黄シランカップリング剤及び含硫黄加硫促進剤からなる群から選ばれる少なくとも1種である上記1又は2に記載のゴム組成物。
4. 前記無機充填剤がシリカであり、前記含硫黄配合剤が少なくとも含硫黄シランカップリング剤を含み、前記含硫黄シランカップリング剤の量が、前記ジエン系ゴム100質量部に対して1~15質量部である上記1~3のいずれかに記載のゴム組成物。
5. 上記1~4のいずれかに記載のゴム組成物をキャップトレッドに使用する空気入りタイヤ。
本発明のゴム組成物は、硫黄架橋可能なジエン系ゴム100質量部に対して、カーボンブラック1~100質量部及び/又は無機充填材10~150質量部と、含硫黄配合剤1~30質量部と、スズオキサイド化合物0.1~20質量部とを配合してなるゴム組成物である。
スズオキサイド化合物の構造において>Sn=Oを構成するスズは、一般的なスズ化合物同様に、含硫黄シランカップリング剤とシリカの縮合反応を促進する。さらに、>Sn=O結合を持たない一般的な4価の有機スズ化合物と比較してその求電子性(特にp軌道における求電子性)が高く、酸素や硫黄などの非共有電子対を有する元素と相互作用しやすい。また、スズオキサイド化合物においてスズ原子の周辺の空間が比較的大きく立体障害が小さいため硫黄などの高周期(原子半径が大きい。)元素とも相互作用しやすい。一方、一般的な2価のスズ化合物と比較して、スズオキサイド化合物は、ポリスルフィド結合からの脱硫反応による失活が起きにくいため、スズオキサイド化合物によって、含硫黄配合剤-ゴムの化学反応が効率的に促進され、その結果、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスに優れるゴムを、加工性を悪化させることなく得ることが可能となったと考えられる。なお上記メカニズムは本願発明者の推測であり上記メカニズム以外であっても本願発明の範囲内である。
芳香族ビニル-共役ジエン共重合体ゴムとしては、例えば、スチレン-ブタジエン共重合体ゴム(SBR)、スチレン-イソプレン共重合体ゴムなどが挙げられる。なかでも、ウェットグリップ性能により優れたタイヤが得られる理由から、スチレン-ブタジエン共重合体ゴム(SBR)であることが好ましい。
ジエン系ゴムの重量平均分子量は、加工性、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、200,000~2,500,000であるのが好ましい。本発明において、ジエン系ゴムの重量平均分子量(Mw)は、テトラヒドロフランを溶媒とするゲルパーミエーションクロマトグラフィー(GPC)により標準ポリスチレン換算により測定するものとする。
ジエン系ゴムはその製造について特に制限されない。例えば、従来公知のものが挙げられる。ジエン系ゴムはそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
本発明において、カーボンブラックの量は、硫黄架橋可能なジエン系ゴム100質量部に対して1~100質量部である。カーボンブラックの量は、加工性、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、ジエン系ゴム100質量部に対して、3~90質量部であるのが好ましく、5~80質量部であるのがより好ましい。
シリカとしては、例えば、湿式シリカ、乾式シリカ、ヒュームドシリカ、珪藻土などが挙げられる。シリカは、ゴムの補強性の観点から湿式シリカを含むことが好ましい。
ここで、CTAB吸着比表面積は、シリカがシランカップリング剤との吸着に利用できる表面積の代用特性であり、シリカ表面へのCTAB吸着量をJIS K6217-3:2001「第3部:比表面積の求め方-CTAB吸着法」にしたがって測定した値である。
無機充填剤はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
無機充填剤がシリカである場合、含硫黄配合剤が少なくとも含硫黄シランカップリング剤を含むのが、低発熱性、加工性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、好ましい態様の1つとして挙げられる。
なかでも、低発熱性、加工性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、硫黄原子が2個以上のポリスルフィド結合を有するポリスルフィド系シランカップリング剤が好ましく、硫黄原子が2~5個のポリスルフィド結合を有するポリスルフィド系シランカップリング剤がより好ましく、ビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィドがさらに好ましい。
ポリスルフィド結合は、2つの炭素原子の間に硫黄原子を2つ及び/又はそれ以上の複数個有する結合である。炭素原子に結合する硫黄原子は脱硫しにくく、両側に硫黄原子が結合する硫黄原子は脱硫しやすい。本発明において、スズオキサイド化合物は硫黄原子が3個以上のポリスルフィド系シランカップリング剤から硫黄原子が脱硫することによるスズオキサイド化合物の失活を適度に抑制し、かつ、含硫黄配合剤-ゴムの化学反応(例えば、硫黄-ゴム、含硫黄加硫促進剤-ゴム、シリカ-含硫黄シランカップリング剤-ゴムの化学反応)を促進し、このことによって、より優れた、低発熱性、加工性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスに寄与すると本願発明者は推察する。なかでも、シリカ-含硫黄シランカップリング剤-ゴムの化学反応が特に促進され、詳細にはシリカ-含硫黄シランカップリング剤の縮合反応、含硫黄シランカップリング剤-ゴムの架橋反応の二つを同時にバランスよく促進すると考えられる。
なかでも、加工性、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド、N,N-ジシクロヘキシル-2-ベンゾチアゾリルスルフェンアミドが好ましい。
含硫黄配合剤はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
硫黄の量はジエン系ゴム100質量部に対して0.1~10質量部であるのが好ましい。
含硫黄加硫促進剤の量はジエン系ゴム100質量部に対して0.1~10質量部であるのが好ましい。
含硫黄シランカップリング剤の量は、加工性、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、ジエン系ゴム100質量部に対して、1~15質量部であるのが好ましく、3~12質量部であるのがより好ましい。
スズオキサイド化合物は有機基を有することができる。有機基はスズ原子に結合するのが好ましい態様の1つとして挙げられる。有機基としては、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有することができる炭化水素基が挙げられる。炭化水素基は、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられ、直鎖状、分岐状のいずれでもよく、不飽和結合を有してもよい。具体的には、例えば、置換基を有してもよい、炭素数1~20の炭化水素基、炭素数1~20のアルコキシ基、-NRR′基(前記R、前記R′はそれぞれ独立に炭素数1~20の炭化水素基及び/又は水素である。)が挙げられる。置換基としては、例えば、ヒドロキシ基、カルボキシル基、シアノ基、アミノ基、ハロゲンなどが挙げられる。
また、スズオキサイド化合物は、スズ原子に、例えば、ヒドロキシ基(-OH基)、アミノ基(-NH2基)、ハロゲン(例えば、-F、-Cl、-Br、-I)のような官能基、水素(-H)が結合するのが好ましい態様の1つとして挙げられる。
炭素数1~20のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、オクチルオキシ基、デシルオキシ基、ドデシルオキシ基が挙げられる。
-NRR′基において、R、R′はそれぞれ独立に置換基を有してもよい、炭素数1~20の炭化水素基、又は水素であり、置換基を有してもよい、炭素数1~20の炭化水素基は上記と同様である。-NRR′基としては、例えば、ジメチルアミノ基、ジエチルアミノ基、ジシクロヘキシル基、ジフェニル基、アミノ基などが挙げられる。
ハロゲンとしては、例えば、-F、-Cl、-Br、-Iが挙げられる。
スズオキサイド化合物は、式(1)で表される化合物を少なくとも含むものとすることができる。
また、無機充填剤がシリカである場合、本発明のゴム組成物が、硫黄を含まないシランカップリング剤をさらに配合するのが好ましい態様の1つとして挙げられる。
硫黄を含まないシランカップリング剤は特に制限されない。例えば、アミノシランカップリング剤、エポキシシランカップリング剤、ヒドロキシシランカップリング剤が挙げられる。
また、硫黄を含まないシランカップリング剤及の量は、加工性、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスにより優れるという観点から、ジエン系ゴム100質量部に対して、1~15質量部であるのが好ましく、3~12質量部であるのがより好ましい。
添加剤としては、例えば、本発明のゴム組成物に含有される、酸化亜鉛、ステアリン酸、老化防止剤、加工助剤、アロマオイル、液状ポリマー、テルペン系樹脂、熱硬化性樹脂、硫黄以外の加硫剤、硫黄原子を有さない加硫促進剤、硫黄原子を有さない加硫促進助剤など、ゴム組成物に一般的に使用される各種添加剤が挙げられる。
また、本発明のゴム組成物は、従来公知の加硫または架橋条件で加硫または架橋することができる。
本発明のゴム組成物は例えば、タイヤ、ベルト、ホースなどに使用することができる。
本発明の空気入りタイヤは、本発明のゴム組成物をキャップトレッドに使用する空気入りタイヤである。本発明において使用されるゴム組成物は本発明のゴム組成物であれば特に制限されない。本発明の空気入りタイヤが有するキャップトレッドは本発明のゴム組成物を使用して製造される。
図1は、本発明の空気入りタイヤの実施形態の一例について、そのタイヤ子午線方向の部分断面を模式的に表す断面図である。図1において、符号1はキャップトレッド、符号2はサイドウォール、符号3はビードである。
キャップトレッド1が本発明のゴム組成物により構成されている。
<未加硫ゴム組成物の製造>
表1、表2に示す配合(質量部)において、加硫系(加硫促進剤、硫黄)を除く成分を1.7リットルの密閉式バンバリーミキサーで5分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物をオープンロールで、加硫系を加えて混練し、未加硫ゴム組成物を得た。
<加硫ゴムの製造>
次に上述のとおり得られた未加硫ゴム組成物を所定の金型中で160℃で20分間プレス加硫して加硫ゴム試験片を調製した。
上述のとおり得られた、未加硫ゴム組成物、加硫ゴム試験片について以下に示す試験法で物性を測定した。結果を表1、表2に示す。表1において、結果は比較例1の値を100とする指数で示される。表2において、結果は比較例8の値を100とする指数で示される。
・tanδの測定
岩本製作所(株)製の粘弾性スペクトロメーターを用い、伸張変形歪率10±2%、振動数20Hz、温度0℃、50℃、条件にて加硫ゴム試験片についてtanδを測定した。tanδ(0℃)は指数が大きいほどウェットグリップ性能に優れることを示す。tanδ(50℃)は指数が小さいほど低発熱性であることを示す。
・引張応力(モジュラス)、引張強度(破断強度、TB)、破断伸び(EB)の測定
加硫ゴム試験片からJIS3号ダンベル状の試験片を打ち抜き、引張速度500mm/分での引張試験をJIS K6251に準拠して行い、加硫ゴム試験片の100%モジュラス、引張強度、破断伸びを室温にて測定した。指数の値が大きいほど、モジュラス、引張強度、破断伸びが良好なことを示す。
・ビスの測定
JIS K6300に準拠して、L形ローターを使用し、未加硫ゴム組成物のムーニー粘度ML(1+4)100℃を求めた。指数の値が小さいほど未加硫ゴム組成物の粘度が低く良好なことを示す。
・スコーチ時間の測定
JIS K6300に準拠して、125℃にて未加硫ゴム組成物の粘度が5ポイント上昇する時間(分)を測定した。指数の値が大きいほど加工性が良好なことを示す。
・E-SBR:乳化重合SBR Nipol1502、日本ゼオン社製
・ジ-n-オクチルスズオキサイド:下記式で表される化合物、北興化学工業社製DOTO
・ジ-n-オクチルスズジクロライド:(n-C8H17)2SnCl2、北興化学工業社製DOTC
・ビス(2-エチルヘキサン酸)スズ:キシダ化学社製
・シリカ:湿式シリカ、日本シリカ社製ニップシールAQ、CTAB吸着比表面積170m2/g
・カーボンブラック:昭和キャボット社製ショウブラックN339M
・酸化亜鉛:正同化学社製亜鉛華3号
・ステアリン酸:日本油脂社製ステアリン酸
・老化防止剤:老化防止剤(S-13)、住友化学社製アンチゲン6C
・含硫黄シランカップリング剤:ビス(トリエトキシシリルプロピル)テトラスルフィド。ポリスルフィドとして-S4-を有する。-S4-の両端は炭素原子と結合する。エボニック・デグサ社製Si69
・オイル:昭和シェル石油社製エクストラクト4号S
・イオウ:軽井沢精錬所社製油処理硫黄
・含硫黄加硫促進剤(CZ):N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド、三新化学社製サンセラーCM-PO
・加硫促進剤(DPG):ジフェニルグアニジン、三新化学社製サンセラーD-G
これに対して、実施例1~4は、加工性を悪化させることなく、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスに優れる。
これに対して、実施例5、6は、加工性を悪化させることなく、低発熱性、ウェットグリップ性能、破壊強度、破断伸び、モジュラスに優れる。
2 サイドウォール
3 ビード
4 カーカス
5 ビードコア
6 ビードフィラー
7 インナーライナー
8 ベルト
9 ベルトカバー
12 キャップトレッドゴム層
13 サイドゴム層
14 リムクッションゴム層
Claims (5)
- 硫黄架橋可能なジエン系ゴム100質量部に対して、カーボンブラック1~100質量部及び/又は無機充填材10~150質量部と、含硫黄配合剤1~30質量部と、スズオキサイド化合物0.1~20質量部とを配合してなるゴム組成物。
- 前記含硫黄配合剤が、硫黄、含硫黄シランカップリング剤及び含硫黄加硫促進剤からなる群から選ばれる少なくとも1種である請求項1又は2に記載のゴム組成物。
- 前記無機充填剤がシリカであり、前記含硫黄配合剤が少なくとも含硫黄シランカップリング剤を含み、前記含硫黄シランカップリング剤の量が、前記ジエン系ゴム100質量部に対して1~15質量部である請求項1~3のいずれかに記載のゴム組成物。
- 請求項1~4のいずれかに記載のゴム組成物をキャップトレッドに使用する空気入りタイヤ。
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US20150314645A1 (en) | 2015-11-05 |
JP2014080480A (ja) | 2014-05-08 |
DE112013005001T5 (de) | 2015-07-02 |
JP5975836B2 (ja) | 2016-08-23 |
US9724967B2 (en) | 2017-08-08 |
DE112013005001B4 (de) | 2020-06-25 |
DE112013005001T9 (de) | 2015-10-29 |
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