WO2023047669A1 - 重荷重タイヤ用ゴム組成物 - Google Patents
重荷重タイヤ用ゴム組成物 Download PDFInfo
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- WO2023047669A1 WO2023047669A1 PCT/JP2022/015257 JP2022015257W WO2023047669A1 WO 2023047669 A1 WO2023047669 A1 WO 2023047669A1 JP 2022015257 W JP2022015257 W JP 2022015257W WO 2023047669 A1 WO2023047669 A1 WO 2023047669A1
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- Prior art keywords
- mass
- rubber
- silica
- blended
- rubber composition
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- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
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- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
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- SECPZKHBENQXJG-BQYQJAHWSA-N palmitelaidic acid Chemical compound CCCCCC\C=C\CCCCCCCC(O)=O SECPZKHBENQXJG-BQYQJAHWSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- DGPCSURYVBYWAT-UHFFFAOYSA-N propane-1,2,3-triol;tetradecanoic acid Chemical compound OCC(O)CO.CCCCCCCCCCCCCC(O)=O DGPCSURYVBYWAT-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of 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
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a rubber composition for heavy duty tires intended primarily for use in heavy duty tires.
- silica is compounded in a rubber component mainly composed of natural rubber, and a specific silane coupling agent is compounded to improve the dispersion of silica, thereby improving wear resistance and low rolling resistance. It is proposed to improve resistance.
- environmental regulations for heavy-duty tires have become stricter, and requirements for fuel efficiency performance have become more sophisticated. Therefore, there is a demand for further measures to improve wear resistance, fuel efficiency, processability, and tensile strength in rubber compositions for heavy-duty tires.
- An object of the present invention is to provide a rubber composition for heavy-duty tires that has improved wear resistance and fuel efficiency over conventional levels, and that has good processability and tensile strength, and that achieves both of these properties in a well-balanced manner. That's what it is.
- the rubber composition for tires of the present invention that achieves the above object comprises 60% by mass to 85% by mass of isoprene rubber and 15% by mass to 40% by mass of modified styrene-butadiene rubber having a glass transition temperature of less than -50°C. 40 parts by mass or more of silica is blended with respect to 100 parts by mass of the diene rubber, and 1% by mass to 20% by mass of the silane coupling agent is blended with respect to the amount of silica blended. .
- the rubber composition for heavy-duty tires of the present invention uses specific amounts of an isoprene-based rubber and a modified styrene-butadiene rubber having a glass transition temperature of less than ⁇ 50° C. as rubber components, and Since specific amounts of silica and a silane coupling agent are blended, wear resistance and fuel efficiency performance can be improved beyond conventional levels.
- a modified styrene-butadiene rubber having a glass transition temperature of less than ⁇ 50° C. is used in combination, it is possible to improve fuel efficiency performance while improving abrasion resistance.
- the silica and the silane coupling agent are blended in appropriate amounts, respectively, the silica can be dispersed well, and both wear resistance and fuel efficiency can be effectively achieved.
- the rubber composition for heavy duty tires of the present invention it is preferable to blend 3.0% by mass to 10% by mass of zinc oxide with respect to the amount of silica blended.
- the rubber composition for heavy duty tires of the present invention it is preferable to blend 1% by mass to 20% by mass of glycerin fatty acid ester and/or glycerin fatty acid metal salt relative to the amount of silica compounded.
- glycerin fatty acid ester and/or glycerin fatty acid metal salt By blending a specific amount of glycerin fatty acid ester and/or glycerin fatty acid metal salt in this way, it is possible to improve the dispersibility of silica in rubber, which is advantageous for achieving both wear resistance and fuel efficiency. become.
- the viscosity of the rubber composition can be moderately lowered and the dispersion can be improved, so that the rubber composition has low fuel consumption and Machinability can be improved.
- the rubber composition for heavy duty tires of the present invention 1 to 20 parts by mass of carbon black having a nitrogen adsorption specific surface area N 2 SA of 65 to 120 m 2 /g is added to 100 parts by mass of diene rubber. It is preferable to mix parts by mass. By blending carbon black having a specific particle size in this manner, the rubber can be blackened without exacerbating heat generation.
- the rubber component contains not only isoprene-based rubber and modified styrene-butadiene rubber having a glass transition temperature of less than ⁇ 50° C., but also modified polybutadiene rubber, thereby further improving abrasion resistance and fuel efficiency. can be done.
- heavy duty tires refer to large tires that are mounted on trucks, buses, and construction vehicles.
- the heavy duty tire referred to in the present invention is preferably a pneumatic tire, but may be a non-pneumatic tire.
- a pneumatic tire can be filled with air, an inert gas such as nitrogen, or other gas.
- a rubber composition for a heavy duty tire refers to a rubber composition forming a component of a heavy duty tire, preferably a tread rubber.
- the rubber component necessarily contains an isoprene-based rubber and a modified styrene-butadiene rubber.
- modified polybutadiene rubber can be used together.
- isoprene-based rubbers examples include various natural rubbers, epoxidized natural rubbers, and various synthetic polyisoprene rubbers.
- isoprene-based rubber a rubber commonly used in rubber compositions for tires can be used.
- the content of the isoprene rubber is 60% by mass to 85% by mass, preferably 65% by mass to 75% by mass, when the entire diene rubber is 100% by mass.
- a specific amount of isoprene-based rubber in this manner, a good balance between wear resistance and fuel efficiency can be achieved. If the isoprene-based rubber content is less than 60% by mass, chipping resistance deteriorates. If the isoprene-based rubber content exceeds 85% by mass, the fuel efficiency is lowered.
- the modified styrene-butadiene rubber used in the present invention has a glass transition temperature of less than -50°C, preferably -65°C to -50°C.
- a modified styrene-butadiene rubber having a specific glass transition temperature in this way, it is possible to improve fuel efficiency performance while improving abrasion resistance.
- the content of the modified styrene-butadiene rubber is 15% by mass to 40% by mass, preferably 25% by mass to 35% by mass, based on 100% by mass of the whole diene rubber.
- By containing a specific amount of modified styrene-butadiene rubber in this way it is possible to effectively exhibit the aforementioned effect of achieving both wear resistance and fuel efficiency.
- the content of the modified styrene-butadiene rubber is less than 15% by mass, the fuel efficiency deteriorates. If the content of the modified styrene-butadiene rubber exceeds 40% by mass, the tensile strength decreases.
- the styrene content of the modified styrene-butadiene rubber used in the present invention is preferably 25% by mass or less, more preferably 20% by mass or less. Further, the modified styrene-butadiene rubber used in the present invention preferably has a vinyl content of 25% by mass or more, more preferably 35% by mass or more. When the styrene content is within the above range, good abrasion resistance can be achieved. Also, when the vinyl content is within the above range, fuel efficiency can be improved.
- the styrene content and vinyl content are each measured by infrared spectroscopic analysis (Hampton method). The styrene content and the vinyl content in the modified styrene-butadiene rubber can be appropriately adjusted by ordinary methods such as catalysts.
- the molecular weight distribution represented by the ratio Mw/Mn between the weight average molecular weight Mw and the number average molecular weight Mn of the modified styrene-butadiene rubber used in the present invention is preferably 4.0 or less, more preferably 2.5 or less. good.
- Mw/Mn polystyrene-equivalent values measured by gel permeation chromatography (GPC).
- modified styrene-butadiene rubber rubbers that are commonly used in rubber compositions for tires can be used.
- terminal-modified styrene-butadiene rubber in which one or both ends of the molecular chain are modified with an organic compound having a functional group can be exemplified.
- styrene-butadiene rubber before modification either solution-polymerized styrene-butadiene rubber or emulsion-polymerized styrene-butadiene rubber can be used.
- the type of functional group is not particularly limited, but from the viewpoint of improving the dispersibility of silica, it is preferable to employ one having reactivity with the silanol group on the silica surface.
- functional groups that react with silanol groups include hydroxyl group-containing polyorganosiloxane structures, alkoxysilyl groups, hydroxyl groups (hydroxyl groups), aldehyde groups, carboxyl groups, amino groups, imino groups, epoxy groups, amide groups, thiol groups, Ether groups may be mentioned. Among them, it is preferably at least one selected from a hydroxyl group (hydroxyl group), an amino group, and an alkoxyl group.
- modified polybutadiene rubber can optionally be used together as a rubber component constituting the rubber composition for heavy-duty tires of the present invention.
- tensile strength can be improved, and these can be achieved in a well-balanced manner.
- its content is preferably 1% by mass to 20% by mass, more preferably 10% by mass to 20% by mass, when the entire diene rubber is 100% by mass. If the content of the modified polybutadiene rubber is less than 1% by mass, the modified polybutadiene rubber is not substantially included, so that the combined use of the modified polybutadiene rubber cannot be expected to have an effect. If the content of the modified polybutadiene rubber exceeds 20% by mass, the tensile strength decreases.
- modified polybutadiene rubber rubbers that are commonly used in rubber compositions for tires can be used.
- terminal-modified polybutadiene rubber modified with an organic compound having a functional group at one or both ends of the molecular chain can be exemplified.
- the type of functional group is not particularly limited, but from the viewpoint of improving the dispersibility of silica, it is preferable to employ one having reactivity with the silanol group on the silica surface.
- Examples of functional groups that react with silanol groups include hydroxyl group-containing polyorganosiloxane structures, alkoxysilyl groups, hydroxyl groups (hydroxyl groups), aldehyde groups, carboxyl groups, amino groups, imino groups, epoxy groups, amide groups, thiol groups, Ether groups may be mentioned. Among them, it is preferably at least one selected from a hydroxyl group (hydroxyl group), an amino group, and an alkoxyl group.
- Silica is always blended in the rubber composition for heavy-duty tires of the present invention.
- Silica that is commonly used in rubber compositions for tires can be used.
- wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. may be mentioned, and these may be used alone or in combination of two or more.
- the amount of silica compounded is 40 parts by mass or more, preferably 45 to 60 parts by mass, per 100 parts by mass of the rubber component. By blending a sufficient amount of silica in this manner, wear resistance and fuel efficiency performance can be improved. If the silica content is less than 40 parts by mass, the effect of improving wear resistance and fuel efficiency cannot be sufficiently expected.
- the CTAB adsorption specific surface area of silica used in the present invention is not particularly limited, it is preferably 120 m 2 /g to 230 m 2 /g, more preferably 140 m 2 /g to 175 m 2 /g. If the CTAB adsorption specific surface area of silica is less than 120 m 2 /g, the effect of improving wear resistance and low rolling resistance may not be obtained sufficiently. Further, if the CTAB adsorption specific surface area of silica exceeds 230 m 2 /g, there is a possibility that workability will deteriorate. In this specification, the CTAB adsorption specific surface area of silica is a value measured according to ISO 5794.
- a silane coupling agent is always blended together with silica.
- silane coupling agent is not particularly limited as long as it can be used in silica-blended rubber compositions.
- Sulfur-containing silane coupling agents such as triethoxysilylpropyl)disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, ⁇ -mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane can be exemplified. .
- the blending amount of the silane coupling agent is 1% by mass to 20% by mass, preferably 5% by mass to 15% by mass, based on the above-described silica blending amount. If the compounded amount of the silane coupling agent is less than 1% by mass of the silica compounded amount, the dispersion of silica cannot be sufficiently improved. If the compounded amount of the silane coupling agent exceeds 20% by mass of the silica compounded amount, the silane coupling agents will condense with each other, making it impossible to obtain the desired tensile strength in the rubber composition.
- the nitrogen adsorption specific surface area N 2 SA is preferably 65 m 2 /g to 120 m 2 /g, more preferably 65 m 2 /g to 100 m 2 /g. It is advantageous to improve the abrasion resistance by using carbon black having an appropriate particle size in combination. If the nitrogen adsorption specific surface area N 2 SA of carbon black is less than 65 m 2 /g, the effect of improving wear resistance cannot be sufficiently expected. When the nitrogen adsorption specific surface area N 2 SA of carbon black exceeds 120 m 2 /g, it becomes difficult to ensure workability.
- the nitrogen adsorption specific surface area N 2 SA of carbon black shall be measured according to JIS K6217-2.
- the amount is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, per 100 parts by mass of the rubber component. If the amount of carbon black is less than 1 part by mass, the rubber cannot be blackened. If the amount of carbon black to be blended exceeds 20 parts by mass, the fuel economy will deteriorate.
- the rubber composition for heavy-duty tires of the present invention can also contain inorganic fillers other than the aforementioned silica and carbon black.
- inorganic fillers include clay, talc, calcium carbonate, mica, and aluminum hydroxide.
- the rubber composition for heavy-duty tires of the present invention it is preferable to blend zinc oxide together with the aforementioned silica.
- a suitable crosslinked state can be maintained, which is advantageous for achieving both wear resistance and fuel efficiency.
- Zinc oxide that is commonly used in rubber compositions for tires can be blended.
- the content of zinc oxide is 2.5% by mass or more, preferably 3.0% to 10% by mass, more preferably 3.0% to 7.0% by mass, based on the above-described silica content. is.
- the amount of zinc oxide is less than 2.5% by mass of the amount of silica, reversion occurs, resulting in poor fuel efficiency and wear resistance.
- the compounded amount of zinc oxide exceeds 10% by mass of the compounded amount of silica, vulcanization slows down, resulting in poor productivity.
- a glycerin fatty acid ester and/or a glycerin fatty acid metal salt together with the silica described above.
- the two —OH groups derived from glycerin are adsorbed to the silanol groups on the surface of the silica, and at the same time, the carbon chain derived from the fatty acid becomes hydrophobic. Acting as a site, it can reduce the viscosity of the rubber composition and improve the dispersibility of silica in the rubber. As a result, both wear resistance and fuel economy performance can be achieved, and the tensile strength and workability of the rubber composition can be improved.
- the amount of glycerin fatty acid ester and/or glycerin fatty acid metal salt to be blended is preferably 1% to 20% by mass, more preferably 3% to 10% by mass, relative to the aforementioned amount of silica. More specifically, when either the glycerin fatty acid ester or the glycerin fatty acid metal salt is blended alone, the blending amount is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 20% by mass, based on the above-described silica blending amount. should be 3% by mass to 10% by mass.
- the individual blending amounts are preferably as described above, but the total blending amount of both is preferably less than the above-described silica blending amount. should be 2% to 20% by mass, more preferably 3% to 10% by mass.
- the total amount of these formulations is the same as in the case of blending both glycerin fatty acid esters and glycerin fatty acid metal salts. Do the same.
- the amount of the glycerin fatty acid ester and/or the glycerin fatty acid metal salt to be blended is less than 1% by mass relative to the mass of the silica, the blending amount is too small to achieve the effects of the present invention. If the amount of glycerin fatty acid ester and/or glycerin fatty acid metal salt to be blended exceeds 20% by mass relative to the mass of silica, the plasticizing effect deteriorates the tensile strength.
- a glycerin fatty acid ester is a compound obtained by ester-bonding a fatty acid to polyglycerin.
- the glycerin fatty acid metal salt is a metal salt of the aforementioned glycerin fatty acid ester (a compound obtained by ester-bonding a fatty acid to polyglycerin).
- Polyglycerin is obtained by dehydration condensation of glycerins.
- the degree of polymerization of glycerin in the polyglycerin portion is not particularly limited, but is preferably 2-10, more preferably 3-9.
- the fatty acid is preferably a saturated or unsaturated aliphatic carboxylic acid having 2 to 24 carbon atoms, more preferably 4 to 20 carbon atoms, and may have a substituent other than the carboxy group.
- Substituents other than the carboxy group include, for example, a hydroxy group, an amino group, a phosphoric acid group, a thiocarboxyl group, a mercapto group, a nitrile group and the like.
- the fatty acid when it has a hydroxy group, it may be a condensate in which fatty acids are ester-bonded to each other.
- fatty acids examples include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecane.
- glycerin fatty acid esters include polyglycerin laurate, polyglycerin stearate, polyglycerin oleate, polyglycerin erucate, polyglycerin behenate, polyglycerin condensed ricinoleate, poly Glycerin myristate, polyglycerin linoleate, and the like can be mentioned. These glycerin fatty acid esters can be used alone or as any blend.
- Examples of metals in the above-mentioned glycerin fatty acid metal salt include alkali metals, alkaline earth metals, transition metals (group 3-11 metals), aluminum, germanium, tin, antimony, and the like.
- alkali metals lithium, potassium, sodium, etc.
- alkaline earth metals beryllium, magnesium, calcium, strontium, barium, etc.
- magnesium is more preferred.
- the rubber composition for heavy-duty tires of the present invention contains various additives commonly used in rubber compositions for tires, such as vulcanizing or crosslinking agents, vulcanization accelerators, various oils, anti-aging agents, and plasticizers. , can be blended within a range that does not hinder the object of the present invention. Further, these additives can be kneaded by a common method to form a rubber composition and used for vulcanization or crosslinking. The blending amount of these additives can be a conventional general blending amount as long as it does not contradict the object of the present invention.
- the rubber composition for tires can be produced by mixing the above components using a common rubber kneading machine such as a Banbury mixer, a kneader, and a roll.
- the step of mixing each component should preferably include at least two stages. More specifically, it is preferable to include the first step of mixing at a mixing temperature of 147°C or lower and the second step and subsequent steps of mixing at a mixing temperature of 130°C to 150°C. By setting the mixing temperature to such a value, suitable shear can be applied to the rubber composition, and tensile strength and abrasion resistance can be improved. Moreover, it is preferable to add and mix materials other than at least carbon black in the first stage, and to add and mix carbon black in the second and subsequent stages. By adding carbon black in the second and subsequent stages in this way, the dispersibility of silica can be improved and the overall mixing time can be shortened, so that both low fuel consumption and productivity can be achieved.
- the obtained rubber composition for tires was evaluated for workability, tensile strength, fuel efficiency performance, and wear resistance performance by the methods shown below.
- Tensile Strength Using the obtained tire rubber composition, vulcanization was performed at 145° C. for 35 minutes using a mold of a predetermined shape to prepare a vulcanized rubber test piece of each tire rubber composition. A JIS No. 3 dumbbell-shaped test piece was cut out from the obtained vulcanized rubber test piece according to JIS K6251, and a tensile test was performed according to JIS K6251 under the conditions of a temperature of 20° C. and a tensile speed of 500 mm/min. Tensile elongation at break was measured and used as an index of tensile strength. The evaluation results are shown as indices with the value of Standard Example 1 being 100. A larger index value means better tensile strength and better chipping resistance when used as a heavy-duty tire.
- vulcanization was performed at 145° C. for 35 minutes using a mold of a predetermined shape to prepare a vulcanized rubber test piece of each tire rubber composition.
- the tan ⁇ at 60°C of the obtained vulcanized rubber test piece was measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. under conditions of an initial strain of 10%, an amplitude of ⁇ 2%, a frequency of 20 Hz, and a temperature of 60°C.
- the evaluation results are shown as indices with the value of Standard Example 1 being 100. A smaller index value means better fuel economy performance.
- Abrasion Resistance Eighteen types of tire rubber compositions (Standard Example 1, Comparative Examples 1 to 6, and Examples 1 to 11) having the formulations shown in Tables 1 and 2 were used as tread rubbers, and the tire size was 11R22. 5 pneumatic tire (test tire) was manufactured. At this time, each portion other than the tread rubber was common to all test tires. These test tires were mounted on a wheel with a rim size of 22.5 x 9.0, mounted on a test vehicle at an air pressure of 230 kPa, and run on a dry road surface for 50,000 km. sex was measured. The evaluation results are shown as indices with the value of Standard Example 1 being 100. The larger the index, the greater the remaining groove depth and the better the wear resistance. If the index value is "95" or more, it means that excellent performance equal to or better than the conventional level was obtained. do.
- Tables 1 and 2 The types of raw materials used in Tables 1 and 2 are shown below.
- - NR natural rubber
- RSS No. 3 ⁇ BR: butadiene rubber
- Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.
- ⁇ SBR Styrene-butadiene rubber
- Nipol 1502 manufactured by Nippon Zeon Co., Ltd.
- Modified SBR2 Modified styrene-butadiene rubber, NS612 manufactured by Nippon Zeon Co., Ltd.
- CB1 carbon black
- Show Black N339 manufactured by Cabot Japan nitrogen adsorption specific surface area N 2 SA: 90 m 2 /g
- CB2 carbon black
- Show Black N550 manufactured by Cabot Japan nitrogen adsorption specific surface area N 2 SA: 39 m 2 /g
- CB3 Carbon black, Niteron #430 manufactured by Nippon Steel Carbon Co., Ltd.
- N 2 SA nitrogen adsorption specific surface area
- Silica Zeosil 1165MP manufactured by Solvay (CTAB adsorption specific surface area: 156 m 2 /g)
- Silane coupling agent bis (3-triethoxysilylpropyl) tetrasulfide, Si69 manufactured by Evonik Degussa Japan
- ⁇ Zinc oxide Three types of zinc oxide manufactured by Seido Chemical Industry Co., Ltd.
- ⁇ Glycerin fatty acid ester Glycerol monostearate manufactured by Sigma-Aldrich
- Steparic acid YR stearate manufactured by NOF Corporation
- Anti-aging agent Santoflex 6PPD manufactured by Solutia Europe
- ⁇ Wax Sannok manufactured by Ouchi Shinko Kagaku Co., Ltd.
- ⁇ Vulcanization accelerator Noccellar CZ-G manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
- ⁇ Sulfur Oil-treated sulfur manufactured by Karuizawa Refinery Co., Ltd.
- the tire rubber compositions of Examples 1 to 11 improved workability, tensile elongation at break, fuel efficiency, and wear resistance to the same level or more than Standard Example 1. These performances are well balanced and highly compatible.
- Comparative Example 1 the rubber component was composed only of natural rubber and did not contain modified styrene-butadiene rubber having a glass transition temperature of less than -50°C, resulting in poor fuel efficiency and wear resistance.
- Comparative Example 2 contained unmodified polybutadiene rubber instead of modified styrene-butadiene rubber having a glass transition temperature of less than ⁇ 50° C., resulting in deterioration in workability, tensile elongation at break, and fuel economy performance.
- Comparative Example 3 contained modified polybutadiene rubber instead of modified styrene-butadiene rubber having a glass transition temperature of less than ⁇ 50° C., resulting in poor workability and tensile elongation at break.
- Comparative Example 4 contained unmodified styrene-butadiene rubber instead of modified styrene-butadiene rubber having a glass transition temperature of less than ⁇ 50° C., resulting in deterioration in tensile elongation at break and fuel efficiency.
- Comparative Example 5 the tensile elongation at break deteriorated because the amount of isoprene-based rubber (natural rubber) blended was small.
- Comparative Example 6 since the amount of silica compounded was small, the wear resistance deteriorated.
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Abstract
Description
得られた各タイヤ用ゴム組成物を使用して、幅250mm、厚さ20mmのゴムシートを押出成形し、押出速度を測定した。評価結果は、標準例1の値を100とする指数で示した。この指数値が大きいほど、加工性に優れることを意味する。
得られたタイヤ用ゴム組成物を用いて、所定形状の金型を用いて145℃、35分間加硫し、各タイヤ用ゴム組成物からなる加硫ゴム試験片を作成した。得られた加硫ゴム試験片から、JIS K6251に準拠して、JIS3号ダンベル形試験片を切り出し、JIS K6251に準拠して、温度20℃、引張速度500mm/分の条件で引張試験を行って引張破断伸びを測定し、引張強度の指標とした。評価結果は、標準例1の値を100とする指数で示した。この指数値が大きいほど、引張強度が良好であり、重荷重タイヤにしたときの耐チッピング性に優れることを意味する。
得られたタイヤ用ゴム組成物を用いて、所定形状の金型を用いて145℃、35分間加硫し、各タイヤ用ゴム組成物からなる加硫ゴム試験片を作成した。得られた加硫ゴム試験片の60℃におけるtanδを、東洋精機製作所社製粘弾性スペクトロメータを用いて、初期歪み10%、振幅±2%、周波数20Hz、温度60℃の条件で測定した。評価結果は、標準例1の値を100とする指数で示した。この指数値が小さいほど、低燃費性能に優れることを意味する。
表1~2に示す配合からなる18種類のタイヤ用ゴム組成物(標準例1、比較例1~6、実施例1~11)をそれぞれトレッドゴムに使用し、タイヤサイズが11R22.5である空気入りタイヤ(試験タイヤ)を製造した。このとき、トレッドゴム以外の各部については、すべての試験タイヤで共通とした。これら試験タイヤについて、リムサイズ22.5×9.0のホイールに組み付けて、空気圧を230kPaとして試験車両に装着し、乾燥路面を5万km走行した後の溝深さを測定することにより、耐摩耗性を測定した。評価結果は、標準例1の値を100とする指数で示した。この指数が大きいほど、残存する溝深さが大きく、耐摩耗性に優れることを意味し、指数値が「95」以上であれば従来レベルと同等以上の優れた性能が得られたことを意味する。
・NR:天然ゴム、RSS No.3
・BR:ブタジエンゴム、日本ゼオン社製 Nipol BR1220
・SBR:スチレンブタジエンゴム、日本ゼオン社製 Nipol 1502
・変性BR:変性ブタジエンゴム、ランクセス社製 CB24
・変性SBR1:変性スチレンブタジエンゴム、ZSE社製 NS616(ガラス転移温度Tg=-23℃、スチレン含有量=22質量%、ビニル含有量=63質量%、Mw/Mn=1.6)
・変性SBR2:変性スチレンブタジエンゴム、日本ゼオン社製 NS612(ガラス転移温度Tg=-61℃、スチレン含有量=15質量%、ビニル含有量=35質量%、Mw/Mn=1.5)
・CB1:カーボンブラック、キャボットジャパン社製 ショウブラックN339(窒素吸着比表面積N2SA:90m2/g)
・CB2:カーボンブラック、キャボットジャパン社製 ショウブラックN550(窒素吸着比表面積N2SA:39m2/g)
・CB3:カーボンブラック、日鉄カーボン社製 ニテロン#430(窒素吸着比表面積N2SA:137m2/g)
・シリカ:Solvay社製 Zeosil 1165MP(CTAB吸着比表面積:156m2/g)
・シランカップリング剤:ビス(3-トリエトキシシリルプロピル)テトラスルフィド、エボニックデグッサジャパン社製 Si69、
・酸化亜鉛:正同化学工業社製 酸化亜鉛3種
・グリセリン脂肪酸エステル:シグマアルドリッチ社製 モノステアリン酸グリセロール・ステアリン酸:日油社製 ステアリン酸YR
・老化防止剤:Solutia Europe社製 Santoflex 6PPD
・ワックス:大内新興化学社製サンノック
・加硫促進剤:大内新興化学工業社製 ノクセラーCZ‐G
・硫黄:軽井沢精錬所社製 油処理イオウ
Claims (5)
- イソプレン系ゴム60質量%~85質量%と、ガラス転移温度が-50℃未満である変性スチレンブタジエンゴム15質量%~40質量%とを含むジエン系ゴム100質量部に対して、シリカが40質量部以上配合され、且つ、前記シリカの配合量に対してシランカップリング剤が1質量%~20質量%配合されたことを特徴とする重荷重タイヤ用ゴム組成物。
- 前記シリカの配合量に対して、酸化亜鉛が3.0質量%~10質量%配合されたことを特徴とする請求項1に記載の重荷重タイヤ用ゴム組成物。
- 前記シリカの配合量に対して、グリセリン脂肪酸エステルおよび/またはグリセリン脂肪酸金属塩が1質量%~20質量%配合されたことを特徴とする請求項1または2に記載の重荷重タイヤ用ゴム組成物。
- 前記ジエン系ゴム100質量部に対して、窒素吸着比表面積N2SAが65m2/g~120m2/gであるカーボンブラックが1質量部~20質量部配合されたことを特徴とする請求項1~3のいずれかに記載の重荷重タイヤ用ゴム組成物。
- 前記ジエン系ゴム100質量%中に変性ポリブタジエンゴムを1質量%~20質量%含有することを特徴とする請求項1~4のいずれかに記載の重荷重タイヤ用ゴム組成物。
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JPH06179732A (ja) * | 1992-09-14 | 1994-06-28 | Goodyear Tire & Rubber Co:The | トラックタイヤトレッド製造に有用なスチレン−ブタジエンゴム |
WO2014098155A1 (ja) * | 2012-12-19 | 2014-06-26 | 株式会社ブリヂストン | ゴム組成物及びそれを用いたタイヤ |
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JP2018145239A (ja) * | 2017-03-02 | 2018-09-20 | 横浜ゴム株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
WO2019044892A1 (ja) * | 2017-09-01 | 2019-03-07 | 株式会社クラレ | 重荷重タイヤ用ゴム組成物およびタイヤ |
JP2019038875A (ja) * | 2017-08-22 | 2019-03-14 | 株式会社ブリヂストン | タイヤ |
JP2019056068A (ja) | 2017-09-21 | 2019-04-11 | 横浜ゴム株式会社 | 重荷重タイヤ用ゴム組成物およびその製造方法 |
JP2020158709A (ja) * | 2019-03-27 | 2020-10-01 | 住友ゴム工業株式会社 | タイヤトレッド用ゴム組成物及びタイヤ |
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JP6179732B2 (ja) | 2014-10-20 | 2017-08-16 | Jfeスチール株式会社 | 石炭または石炭と金属酸化物との混合物の成型方法 |
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Patent Citations (8)
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JPH06179732A (ja) * | 1992-09-14 | 1994-06-28 | Goodyear Tire & Rubber Co:The | トラックタイヤトレッド製造に有用なスチレン−ブタジエンゴム |
WO2014098155A1 (ja) * | 2012-12-19 | 2014-06-26 | 株式会社ブリヂストン | ゴム組成物及びそれを用いたタイヤ |
JP2014196407A (ja) * | 2013-03-29 | 2014-10-16 | 株式会社ブリヂストン | ゴム組成物及びゴム組成物の製造方法 |
JP2018145239A (ja) * | 2017-03-02 | 2018-09-20 | 横浜ゴム株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP2019038875A (ja) * | 2017-08-22 | 2019-03-14 | 株式会社ブリヂストン | タイヤ |
WO2019044892A1 (ja) * | 2017-09-01 | 2019-03-07 | 株式会社クラレ | 重荷重タイヤ用ゴム組成物およびタイヤ |
JP2019056068A (ja) | 2017-09-21 | 2019-04-11 | 横浜ゴム株式会社 | 重荷重タイヤ用ゴム組成物およびその製造方法 |
JP2020158709A (ja) * | 2019-03-27 | 2020-10-01 | 住友ゴム工業株式会社 | タイヤトレッド用ゴム組成物及びタイヤ |
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