WO2023054510A1 - マスターバッチ、マスターバッチの製造方法、タイヤ用ゴム組成物、タイヤ用ゴム組成物の製造方法およびタイヤ用ゴム材料 - Google Patents
マスターバッチ、マスターバッチの製造方法、タイヤ用ゴム組成物、タイヤ用ゴム組成物の製造方法およびタイヤ用ゴム材料 Download PDFInfo
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- WO2023054510A1 WO2023054510A1 PCT/JP2022/036258 JP2022036258W WO2023054510A1 WO 2023054510 A1 WO2023054510 A1 WO 2023054510A1 JP 2022036258 W JP2022036258 W JP 2022036258W WO 2023054510 A1 WO2023054510 A1 WO 2023054510A1
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- tires
- fumed silica
- rubber
- mass
- masterbatch
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 174
- 239000005060 rubber Substances 0.000 title claims abstract description 174
- 239000000203 mixture Substances 0.000 title claims abstract description 102
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 claims abstract description 111
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 47
- 238000004898 kneading Methods 0.000 claims abstract description 45
- 229920003244 diene elastomer Polymers 0.000 claims description 65
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000314 lubricant Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- 229920003049 isoprene rubber Polymers 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 115
- 239000000377 silicon dioxide Substances 0.000 description 41
- 229910021485 fumed silica Inorganic materials 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 238000002156 mixing Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 21
- 239000006229 carbon black Substances 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 238000013329 compounding Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000000945 filler Substances 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000010734 process oil Substances 0.000 description 9
- 239000012763 reinforcing filler Substances 0.000 description 9
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000005372 silanol group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 NipsilAQ Chemical compound 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- IABJHLPWGMWHLX-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-trimethoxysilane Chemical compound C1=CC=C2SC(CCC[Si](OC)(OC)OC)=NC2=C1 IABJHLPWGMWHLX-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000009566 rice Nutrition 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
- 238000010008 shearing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08K5/54—Silicon-containing 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
-
- 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
-
- 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 relates to a masterbatch, a method for producing a masterbatch, a rubber composition for tires, a method for producing a rubber composition for tires, and a rubber material for tires.
- a loss tangent tan ⁇ at 60° C. obtained by measuring the dynamic viscoelasticity of a tire is generally used as an index of tire rolling resistance. The smaller the tan ⁇ at 60°C, the smaller the rolling resistance and the better the fuel efficiency.
- Patent Document 1 discloses compounding wet silica as a filler into a rubber composition for tires in order to reduce rolling resistance. Further, Patent Document 2 discloses adjusting the compounding amount and particle size of carbon black as a filler contained in a rubber composition for tires in order to reduce rolling resistance.
- Patent Document 3 discloses a tire rubber composition having good silica dispersibility in order to sufficiently obtain the effect of reducing the heat buildup of the tire.
- Patent Document 4 discloses a rubber composition for tires capable of improving grip performance, fuel efficiency, friction performance, heat resistance, weather resistance and the like.
- heavy-duty tires used for trucks, buses, etc. are required to have a longer running life than tires for passenger cars. Therefore, heavy-duty tires are required to have not only fuel efficiency and heat resistance, but also high wear resistance.
- the present invention has been made in view of such circumstances, and aims to provide a tire rubber material excellent in abrasion resistance, a masterbatch and a tire rubber composition suitable for producing the same, and a method for producing them. aim.
- the present inventors found that a rubber material for tires having excellent wear resistance can be obtained by blending hydrophilic fumed silica instead of carbon black or wet silica as a filler in a rubber composition for tires. rice field.
- hydrophilic fumed silica is bulkier than wet silica, in a Banbury mixer that is usually used for kneading rubber compositions, scattering of hydrophilic fumed silica tends to occur during kneading, and hydrophilic fumed silica It has been found that it is difficult to obtain a rubber composition in which is sufficiently dispersed.
- the inventors of the present invention conducted further intensive studies, and found that the above knowledge can be solved by using a kneader with a low rotor rotation speed, which is not usually used for kneading rubber compositions, due to the problem of productivity. Found it.
- a method for producing a masterbatch comprising the step of kneading a diene rubber, hydrophilic fumed silica and a silane coupling agent using a kneader.
- the rubber composition for tires according to [8] or [9] comprising the masterbatch according to any one of [1] to [4].
- a method for producing a rubber composition for tires comprising a step of kneading the masterbatch according to any one of [1] to [4] and a diene rubber.
- the rubber material for tires according to [12] obtained by vulcanizing the rubber composition for tires according to any one of [8] to [10].
- FIG. 1 is a process diagram of a method for producing a masterbatch according to this embodiment.
- FIG. 2 is a process diagram of a method for producing a rubber material for tires using the masterbatch according to this embodiment.
- the masterbatch according to this embodiment is a kneaded material used to obtain a rubber material, and contains a diene rubber, hydrophilic fumed silica and a silane coupling agent.
- diene rubber examples include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, ethylene-propylene-diene rubber, chloroprene rubber, and the like. Among these, at least one selected from natural rubber and isoprene rubber is preferable.
- Fumed silica is particulate silicon dioxide produced by high temperature hydrolysis of silicon tetrachloride in an oxyhydrogen flame. Therefore, fumed silica differs from wet silica in its production method, in that the primary aggregates (minimum constituents) of fumed silica have a smaller primary particle size and a larger nitrogen adsorption BET specific surface area than wet silica. Particles of fumed silica are agglomerated and fused in a beaded manner to form bulky agglomerates.
- Fumed silica is divided into hydrophilic fumed silica and hydrophobic fumed silica based on its properties against water.
- Silanol groups are present on the surface of fumed silica.
- a silanol group is chemically active and is particularly reactive with water. Therefore, surface treatment (hydrophobizing treatment) is sometimes performed to reduce reactivity with water by reacting silanol groups with other substances.
- Fumed silica that has been hydrophobized is called hydrophobic fumed silica
- fumed silica that has not been hydrophobized is called hydrophilic fumed silica.
- hydrophobic fumed silica and hydrophilic fumed silica are distinguished by the modified hydrophobicity (M value) shown below.
- Modified hydrophobicity (M value) is a value obtained by a measurement method utilizing the fact that hydrophobic fumed silica floats in water but is completely suspended in methanol. As a method for measuring the M value, the method described in Examples of WO 2004/099075 can be adopted.
- Hydrophobic fumed silica and hydrophilic fumed silica are expressed using the M value. Hydrophobic fumed silica has an M value of 1 or more, and hydrophilic fumed silica has an M value of less than 1.
- the fumed silica contained in the masterbatch according to the present embodiment is hydrophilic fumed silica.
- hydrophilic fumed silica is more likely to form a structure resulting from fumed silica than hydrophobic fumed silica. It is believed that the presence of such a structure in the tire rubber material obtained by vulcanizing the tire rubber composition improves the abrasion resistance of the tire rubber material.
- hydrophobic fumed silica has few such structures and tends to have insufficient improvement in abrasion resistance.
- the tap density of the hydrophilic fumed silica is preferably less than 200 g/L, more preferably 150 g/L or less, even more preferably 100 g/L or less.
- the hydrophilic fumed silica may have a tap density of 200 g / L, but usually, in order to make the hydrophilic fumed silica have a tap density of 200 g / L or more, compression treatment is required. becomes. Therefore, there is a problem that an extra process is required and the cost is increased.
- the lower limit of the tap density of hydrophilic fumed silica is not particularly limited, but from the viewpoint of production, the lower limit of the tap density is, for example, 30 g/L.
- the hydrophilic fumed silica has a BET specific surface area of 50 m 2 /g or more, 80 m 2 /g or more, 120 m 2 /g or more, 200 m 2 /g or more, 250 m 2 /g or more, 300 m 2 /g or more. g or more, preferably 350 m 2 /g or more.
- the BET specific surface area of the fumed silica is within the above range, it is possible to secure a sufficient number of silanol groups in the hydrophilic fumed silica that serve as reaction points with the diene rubber or the silane coupling agent. As a result, the hydrophilic fumed silica and the diene rubber can be well kneaded.
- the upper limit of the BET specific surface area of the hydrophilic fumed silica is not particularly limited, but is, for example, 500 m 2 /g. If the BET specific surface area of the hydrophilic fumed silica is too small, it is necessary to raise the flame temperature during the production of fumed silica, and the structure peculiar to fumed silica is lost, and fumed silica can be stably produced. tend to be unable to If the BET specific surface area of the hydrophilic fumed silica is too large, it tends to be unable to be stably produced.
- the blending amount of hydrophilic fumed silica is 13 parts by mass or more and 130 parts by mass or less with respect to 100 parts by mass of the diene rubber. That is, the masterbatch according to the present embodiment can contain a high concentration of hydrophilic fumed silica that is difficult to knead into diene rubber and difficult to disperse. Therefore, by producing a rubber composition for tires using this masterbatch, a rubber material for tires having excellent wear resistance can be easily obtained.
- the amount of hydrophilic fumed silica compounded is more preferably 15 parts by mass or more, more preferably 20 parts by mass or more with respect to 100 parts by mass of the diene rubber.
- the amount of hydrophilic fumed silica compounded is more preferably 110 parts by mass or less, more preferably 100 parts by mass or less per 100 parts by mass of the diene rubber.
- the blending amount of the hydrophilic fumed silica is too small, the abrasion resistance of the tire rubber material obtained tends to be insufficient. If the blending amount of hydrophilic fumed silica is too large, the hydrophilic fumed silica will not be sufficiently dispersed in the diene rubber, and a good kneaded product will tend not to be obtained.
- silane coupling agent Inclusion of the silane coupling agent in the masterbatch facilitates the formation of a crosslinked structure between the hydrophobic diene rubber and the hydrophilic fumed silica via the silane coupling agent. As a result, the dispersibility of the hydrophilic fumed silica in the masterbatch can be improved, and the wear resistance of the tire rubber material can be improved.
- the silane coupling agent is not particularly limited as long as it is commonly used in rubber compositions.
- sulfur-containing silane coupling agents are preferred.
- Sulfur-containing silane coupling agents include, for example, bis-(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, ⁇ -mercapto Examples include propyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, mercapto-thiocarboxylate oligomers, and the like.
- the silane coupling agent is preferably a blocked mercaptosilane, particularly preferably a mercapto-thiocarboxylate oligomer, from the viewpoint of heat resistance (heat aging resistance) of the tire rubber composition. .
- Mercapto-thiocarboxylate oligomers are oligomers of thiocarboxylates with mercapto groups. Examples of molecular structures of mercapto-thiocarboxylate oligomers are shown below. In the following molecular structure, the sum (x+y) of the repeating number (x) of the bonding unit A and the repeating number (y) of the bonding unit B is preferably in the range of 3-300. Within this range, the mercaptosilane of the bonding unit B is covered by the —C 7 H 15 of the bonding unit A, so that the scorch time can be suppressed from being shortened, and the hydrophilic fumed silica and the diene rubber can be combined. Good reactivity can be ensured.
- a specific example of the mercapto-thiocarboxylate oligomer is “NXT-Z45” manufactured by Momentive.
- the compounding amount of the silane coupling agent is 1 part by mass or more and 40 parts by mass or less per 100 parts by mass of the diene rubber. If the amount of the silane coupling agent is too small, the dispersibility of the hydrophilic fumed silica in the tire rubber composition tends to be insufficient. If the blending amount of the silane coupling agent is too large, the silane coupling agents tend to condense with each other, and the obtained rubber material for tires tends to have insufficient wear resistance.
- the amount of the silane coupling agent compounded is more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the diene rubber.
- the amount of the silane coupling agent compounded is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the diene rubber.
- the compounding amount of the silane coupling agent can be relatively increased as the BET specific surface area of the hydrophilic fumed silica increases. preferable. This is because sufficient reaction points with hydrophilic fumed silica can be secured. Specifically, it is particularly preferable to add the silane coupling agent in the range of 0.33 to 1 mg/m 2 with respect to the specific surface area of the silica to be added.
- the masterbatch may contain, in addition to the above-described components (diene-based rubber, hydrophilic fumed silica and silane coupling agent), components to be blended into the rubber composition.
- examples of such components include lubricants. Including a lubricant in the masterbatch improves the kneadability of the masterbatch.
- lubricants examples include stearic acid and process oil. Lubricants may be used alone or in combination of two or more. Examples of process oil include aroma oil, paraffin oil, naphthenic oil, and the like. These may be used alone or in combination of two or more.
- the blending amount of the lubricant is not limited within the range in which the effects of the present invention can be obtained.
- the blending amount of the lubricant is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the diene rubber.
- the amount of the lubricant compounded is more preferably 2 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the diene rubber.
- the blending amount of the lubricant is more preferably 35 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the diene rubber.
- the blending amount of the lubricant is too small, the kneadability of the masterbatch may be poor, and the abrasion resistance performance of the resulting tire rubber material may not be sufficiently improved. If the blending amount of stearic acid is too large, shear is not applied during kneading, and the hydrophilic fumed silica may not be sufficiently dispersed in the diene rubber.
- the masterbatch may contain reinforcing fillers other than hydrophilic fumed silica.
- reinforcing fillers include carbon black, clay, mica, talc, calcium carbonate, aluminum hydroxide, aluminum oxide and titanium oxide.
- a suitable amount of a filler coupling agent can also be blended.
- the blending amount of the reinforcing filler is not limited within the range in which the effects of the present invention can be obtained, and a general blending amount may be used.
- the masterbatch may contain various additives such as zinc oxide, antioxidants, plasticizers, processing aids, liquid polymers, and thermosetting resins.
- the blending amount of these additives is not limited within the range in which the effect of the present invention can be obtained, and may be a general blending amount.
- the masterbatch according to the present embodiment includes the above-described diene rubber, the above-described hydrophilic fumed silica, the above-described silane coupling agent, and, if necessary, other components, obtained by kneading
- the diene rubber is kneaded using a kneader in order to sufficiently knead the hydrophilic fumed silica and sufficiently disperse the hydrophilic fumed silica in the masterbatch.
- a Banbury mixer has been used to knead silica as a filler into diene-based rubber and sufficiently disperse silica in the masterbatch or rubber composition.
- the Banbury mixer kneads the raw materials by applying high shearing force to the raw materials by rotating the rotor at high speed while pressurizing the mixed raw materials with weights.
- a Banbury mixer is useful when kneading wet silica having a high tap density.
- hydrophilic fumed silica which has a lower tap density and is bulkier than wet silica, is kneaded into diene rubber using a Banbury mixer, the hydrophilic fumed silica tends to scatter. Therefore, there is a problem that the amount of hydrophilic fumed silica that is actually kneaded is less than the target amount. Furthermore, there is a problem that the kneaded hydrophilic fumed silica tends to agglomerate in the masterbatch or rubber composition and is not sufficiently dispersed.
- the present inventors kneaded the hydrophilic fumed silica into the diene rubber using a kneader to suppress the scattering of the hydrophilic fumed silica during kneading, and the kneaded hydrophilic fumed silica.
- a masterbatch in which the silica is well dispersed is obtained.
- a kneader like the Banbury mixer, is a type of internal mixer.
- the difference from the Banbury mixer is the number of rotations of the rotor. From the viewpoint of improving productivity, the rotation speed of the rotor of the Banbury mixer is usually 45 to 80 rpm, whereas the rotation speed of the rotor of the kneader is 20 to 40 rpm.
- the inventors of the present invention have confirmed that the hydrophilic fumed silica cannot be sufficiently kneaded even if kneading is performed by setting the rotor rotation speed of the Banbury mixer to the same level as the rotor rotation speed of the kneader. ing. This is because the Banbury mixer has a rotor rotation speed that is suitable for kneading in the Banbury mixer, and the rotor structure of the Banbury mixer is optimal so that kneading proceeds sufficiently within the set rotor rotation speed range. This is thought to be because the
- the kneader may be a pressurized kneader or an open kneader that does not pressurize.
- a pressurized kneader is preferred in order to sufficiently knead and disperse the hydrophilic fumed silica.
- a pressurized kneader capable of stepwise pressurization control is more preferable.
- the above-described diene rubber, the above-described hydrophilic fumed silica, the above-described silane coupling agent, and, if necessary, other components are put into a kneader and kneaded.
- the rotor speed is 20-40 rpm as described above.
- the kneading time is preferably about 20 to 60 minutes.
- the kneading time of the open kneader is preferably longer than the kneading time of the pressurized kneader.
- a masterbatch is obtained in which the above components are kneaded.
- This masterbatch is a masterbatch containing a high concentration of bulky hydrophilic fumed silica, which is usually difficult to sufficiently knead and disperse.
- the rubber composition for tires according to this embodiment contains a diene rubber, hydrophilic fumed silica, and a silane coupling agent.
- the compounding amount of the hydrophilic fumed silica is 5 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the diene rubber. If the blending amount of the hydrophilic fumed silica is too small, there is a tendency that the obtained rubber material for tires does not have sufficient wear resistance performance. If the blending amount of hydrophilic fumed silica is too large, the hydrophilic fumed silica will not be sufficiently dispersed in the diene rubber, and a good kneaded product will tend not to be obtained.
- the compounding amount of the hydrophilic fumed silica is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, relative to 100 parts by mass of the diene rubber.
- the amount of the hydrophilic fumed silica compounded is preferably 70 parts by mass or less, more preferably 55 parts by mass or less, relative to 100 parts by mass of the diene rubber.
- the range of the BET specific surface area of the hydrophilic fumed silica is preferably the same as the range of the BET specific surface area of the hydrophilic fumed silica contained in the masterbatch described above.
- the compounding amount of the silane coupling agent is 1.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the diene rubber. If the amount of the silane coupling agent is too small, the dispersibility of the hydrophilic fumed silica in the tire rubber composition tends to be insufficient. If the blending amount of the silane coupling agent is too large, the silane coupling agents tend to condense with each other, and the wear resistance of the obtained tire rubber material may not be sufficiently improved.
- the amount of the silane coupling agent compounded is preferably 2.0 parts by mass or more, more preferably 2.5 parts by mass or more, relative to 100 parts by mass of the diene rubber.
- the amount of the silane coupling agent compounded is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the diene rubber.
- the rubber composition for tires according to the present embodiment preferably contains the masterbatch described above. That is, the rubber composition for tires according to the present embodiment is preferably produced using the masterbatch described above. By using the masterbatch described above, it is possible to easily obtain a tire rubber composition containing a predetermined amount of hydrophilic fumed silica that is difficult to knead into and disperse.
- the rubber composition for tires may contain, in addition to the above-described components (diene rubber, hydrophilic fumed silica and silane coupling agent), components blended into the rubber composition.
- the rubber composition for tires may contain process oil.
- process oil include aromatic oil, paraffin oil, naphthenic oil, and the like. These may be used alone or in combination of two or more.
- the blending amount of the process oil is preferably 2 to 10 parts by mass, more preferably 4 to 8 parts by mass, per 100 parts by mass of the diene rubber.
- the rubber composition for tires may contain reinforcing fillers other than hydrophilic fumed silica.
- reinforcing fillers include carbon black, clay, mica, talc, calcium carbonate, aluminum hydroxide, aluminum oxide and titanium oxide.
- an appropriate amount of a filler coupling agent can also be blended.
- the blending amount of these reinforcing fillers may be a general blending amount within the range where the effects of the present invention can be obtained.
- the amount of carbon black compounded is preferably more than 0 parts by mass and 60 parts by mass or less with respect to 100 parts by mass of the diene rubber, for example.
- the rubber composition for tires may contain wet silica as a filler.
- Wet silica is generally silica synthesized by a neutralization reaction between sodium silicate and a mineral acid (usually sulfuric acid). Wet silica is roughly classified into precipitation silica and gel silica. In this embodiment, the wet silica is preferably precipitated silica.
- wet silica has a higher amount of water adsorbed on the silanol groups on the surface than fumed silica. It is believed that this adsorbed water inhibits the formation of a crosslinked structure. Therefore, the amount of wet silica required for the effect resulting from the crosslinked structure via silanol groups is greater than the amount of fumed silica. In other words, when trying to obtain the same effect as that of fumed silica, the blending amount of wet silica is larger than the blending amount of fumed silica.
- wet silica has a smaller BET specific surface area than fumed silica, the amount required to achieve the target hardness of the tire rubber material tends to increase.
- wet silica compounded is small.
- fumed silica is more expensive than wet silica, it is preferable to contain wet silica from the viewpoint of cost.
- the amount of wet silica compounded can be a general compounded amount as long as the effects of the present invention can be obtained.
- it is preferably more than 0 parts by mass and 100 parts by mass or less, more preferably more than 0 parts by mass and 60 parts by mass or less with respect to 100 parts by mass of the diene rubber.
- Wet silica may be mixed with fumed silica before the step of kneading with diene rubber, or may be added in the step of kneading fumed silica and diene rubber.
- Rubber compositions for tires contain vulcanizing agents or cross-linking agents, vulcanization accelerators, sulfur, zinc oxide, stearic acid, anti-aging agents, plasticizers, processing aids, liquid polymers, thermosetting resins, etc. may contain ingredients. Such components can be blended before or after kneading the tire rubber composition to aid vulcanization or cross-linking of the tire rubber composition.
- the compounding amount of these tire components may be a general compounding amount within the range in which the effects of the present invention can be obtained.
- the total amount of sulfur and vulcanization accelerator compounded is preferably 1.5 parts by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the diene rubber.
- the rubber composition for tires according to the present embodiment has excellent wear resistance, and is therefore suitable for heavy-duty tires or tire treads thereof.
- the rubber composition for tires is preferably obtained by kneading the above-described masterbatch, diene-based rubber, and, if necessary, the above-described components. That is, in the present embodiment, the rubber composition for tires is preferably produced by blending other components into the masterbatch. In addition to the diene rubber contained in the masterbatch, a diene rubber is further compounded. On the other hand, the hydrophilic fumed silica is sufficiently contained in the masterbatch and is not blended.
- kneading was performed using a kneader, but the kneader used for kneading the rubber composition for tires is not particularly limited. That is, a Banbury mixer or a kneader may be used. Since kneading is performed using a masterbatch in which hydrophilic fumed silica is sufficiently kneaded and sufficiently dispersed, even if kneading is performed using a Banbury mixer, the hydrophilic fumed silica is kept in a good dispersed state. A kneaded product (rubber composition for tires) is obtained while maintaining the temperature. Although kneading may be performed using a kneader, kneading using a Banbury mixer is preferable from the viewpoint of improving productivity.
- the kneading conditions should be such that the masterbatch and each component are sufficiently kneaded.
- the rubber composition for tires may be produced without using a masterbatch.
- a kneader is used to produce the rubber composition for tires.
- a rubber composition for tires may be produced by charging all the components into a kneader at the same time and kneading them, or by charging each component step by step to produce a rubber composition for tires.
- the rubber material for tires according to the present embodiment is a material obtained by vulcanizing a rubber composition for tires.
- the rubber material for tires is adjusted so that the A hardness of the rubber material for tires is within the range of 55-72 so that the hardness is suitable for tires.
- Common tire rubber materials containing carbon black or wet silica as fillers have a structure in which rubber and carbon black or silica are crosslinked via sulfur, and rubber and carbon black or silica via a silane coupling agent. It has a crosslinked structure and the like. As a result, the A hardness and the crosslink density of the tire rubber material are generally in a proportional relationship.
- the rubber material for tires according to the present embodiment has an A hardness within the range of 55 to 72, and a cross-linking density of 4.0 ⁇ 10 ⁇ 5 mol/mL or more27 by the toluene swelling method of the rubber material for tires. in the range of less than .5 ⁇ 10 ⁇ 5 mol/mL.
- the rubber material for tires according to the present embodiment contains hydrophilic fumed silica derived from the rubber composition for tires described above.
- hydrophilic fumed silica derived from the rubber composition for tires described above.
- this tire rubber material a structure in which the diene rubber and the hydrophilic fumed silica are crosslinked via sulfur, and a structure in which the diene rubber and the hydrophilic fumed silica are crosslinked via a silane coupling agent.
- hydrophilic fumed silica derived from the rubber composition for tires described above.
- a structure in which the diene rubber and the hydrophilic fumed silica are crosslinked via sulfur and a structure in which the diene rubber and the hydrophilic fumed silica are crosslinked via a silane coupling agent.
- the toluene swelling method which is a method for measuring crosslink density
- a structure in which rubber and hydrophilic fumed silica are crosslinked via sulfur and a structure in which rubber and hydrophilic fumed silica are crosslinked via a silane coupling agent
- the crosslinked structure is not soluble in toluene, whereas the structure due to hydrophilic fumed silica is believed to be soluble in toluene.
- this structure contributes to the A hardness but is not reflected in the crosslink density measurements.
- the crosslink density based on the toluene swelling method is higher than that of the tire rubber material containing carbon black, wet silica, or the like. considered low.
- the crosslink density is preferably 27.1 ⁇ 10 ⁇ 5 mol/mL or less. Also, the crosslink density is preferably 6 ⁇ 10 ⁇ 5 mol/mL or more.
- the rubber material for tires has excellent abrasion resistance, it can be suitably used for each member of the tire. Among others, it can be suitably used for treads, base treads, sidewalls, clinches and the like.
- Vehicles to which the rubber material for tires of the present invention can be applied are not particularly limited, but passenger cars, truck buses, construction heavy machinery, EVs, and low-pollution vehicles (eco-cars) that are compatible with global environmental protection require wear resistance. can be suitably applied to
- Example 1 Preparation of masterbatch
- the following components were put into a pressure kneader with a volume of 0.5 L so that the compounded amount per 100 parts by mass of the diene rubber would be the compounded amount shown in Table 1.
- the mixture was kneaded for about 30 minutes at a rotor speed of 20 to 40 rpm and a kneaded product temperature of 130 to 160°C.
- the air cylinder pressure was 0.7 MPa.
- the mixture was cooled to room temperature, and the kneaded material was taken out to obtain a masterbatch.
- D-6 and (D-7) shown below were added to the resulting kneaded mixture and mixed with a 6-inch roll tester to obtain a rubber composition for tires.
- Table 2 shows the formulation of the obtained tire rubber composition.
- a test piece was prepared for the following evaluation of the obtained rubber composition for tires. Using the obtained test piece, the following physical properties were evaluated.
- the hardness (Shore A hardness) of the obtained tire rubber material test piece was measured by a durometer according to JIS K6253 Type A. Since the target A hardness of the tire rubber material is 65, the A hardness of the test piece is preferably around 65 as well. Table 2 shows the results.
- VP (100W1)/(Zxd)
- W1 is the rubber specimen weight.
- Z is the sum of the weight ratios of rubber and compounding agent in the specimen and
- d is the density of the rubber.
- V S is the volume of solvent absorbed by the test piece and is determined from the following formula.
- VS (W2-W3)/ds
- W2 is the weight of the rubber specimen swollen with toluene, and “W3” is the weight of the rubber specimen after drying off the toluene.
- ds is the density of the solvent (toluene).
- ⁇ is the interaction constant between rubber and solvent. In this example, toluene was used as the solvent, so “ ⁇ " was 0.39.
- Example 2 The following components were put into a pressure kneader having a volume of 0.5 L so that the compounding amounts shown in Table 3 were obtained with respect to 100 parts by mass of the diene rubber. After the addition, the mixture was kneaded for about 30 minutes at a rotor speed of 20 to 40 rpm and a kneaded product temperature of 130 to 160°C. The air cylinder pressure was 0.7 MPa. After the kneading was completed, the mixture was cooled to room temperature, and the kneaded material was taken out to obtain a masterbatch.
- D-6 and (D-7) shown below were added to the resulting kneaded mixture and mixed with a 6-inch roll tester to obtain a rubber composition for tires.
- Table 4 shows the formulation of the obtained tire rubber composition.
- a test piece was prepared for the same evaluation as in Experiment 1 for the obtained tire rubber composition. Using the obtained test piece, the physical properties (Mooney viscosity) evaluated in Experiment 1 were evaluated. Table 4 shows the results.
- the obtained rubber composition for tires was vulcanized at 150° C. for 20 minutes using a mold having a thickness of 2 mm, and the obtained vulcanized rubber sheet was punched out with a JIS No. 3 dumbbell to obtain a sample. After heat-aging the sample for 7 days (168 hours) in a gear oven set at a temperature of 80° C., the elongation at break was measured with a tensile tester according to JIS K625-1 together with the unaged sample. The ratio of the elongation at break (Eb) before aging to the elongation at break (Ea) after aging was taken, and Ea/Eb was used as an index of heat aging resistance.
- a rubber material for tires in which the hydrophilic fumed silica has a BET specific surface area of 50 m 2 /g or more exhibits higher heat aging resistance than a rubber material for tires produced using a masterbatch in which carbon black is kneaded. I have confirmed that I have.
- Example 3 The following components were put into a pressure kneader with a volume of 0.5 L so that the compounding amounts shown in Table 5 were obtained per 100 parts by mass of the diene rubber. After the addition, the mixture was kneaded for about 30 minutes at a rotor speed of 20 to 40 rpm and a kneaded product temperature of 130 to 160°C. The air cylinder pressure was 0.7 MPa. After the kneading was completed, the mixture was cooled to room temperature, and the kneaded product was taken out to obtain a rubber composition for tires. That is, in Experiment 3, a rubber composition for tires was produced without using a masterbatch.
- the manufacturing method for the prototypes (B-8) and (B-9) adopted the method described in Surface Science, Vol. 5, No. 1 (1984). Specifically, the flame temperature is converted to an adiabatic temperature calculated from the heat of formation and specific heat in the equilibrium state during the production of fumed silica, and the adiabatic temperature is controlled at 1700 to 1800 ° C. (B-8) and (B-9) hydrophilic fumed silica were produced.
- a test piece was prepared for the same evaluation as in Experiment 1 for the obtained tire rubber composition. Using the obtained test piece, the physical properties (Mooney viscosity) evaluated in Experiment 1 were evaluated. Table 5 shows the results.
- the tire rubber material containing a high concentration of hydrophilic fumed silica without using a masterbatch is a tire rubber material produced using a masterbatch in which carbon black or wet silica is kneaded. It was confirmed that it has higher wear resistance than
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Abstract
Description
[1]ジエン系ゴム100質量部に対して、親水性フュームドシリカを13質量部以上130質量部以下、シランカップリング剤を1質量部以上40質量部以下含むマスターバッチである。
[2]親水性フュームドシリカのBET比表面積が50m2/g以上500m2/g以下である[1]に記載のマスターバッチである。
[3]ジエン系ゴムが、天然ゴムおよびイソプレンゴムからなる群から選ばれる少なくとも1つである[1]または[2]に記載のマスターバッチである。
[4]ジエン系ゴム100質量部に対して、滑剤を1質量部以上40質量部以下含む[1]から[3]のいずれかに記載のマスターバッチである。
[6]親水性フュームドシリカのBET比表面積が50m2/g以上500m2/g以下である[5]に記載のマスターバッチの製造方法である。
[7]さらに、滑剤を混錬する[5]または[6]に記載のマスターバッチの製造方法である。
[9]親水性フュームドシリカのBET比表面積が50m2/g以上500m2/g以下である[8]に記載のタイヤ用ゴム組成物である。
[10][1]から[4]のいずれかに記載のマスターバッチを含む[8]または[9]に記載のタイヤ用ゴム組成物である。
[13][8]から[10]のいずれかに記載のタイヤ用ゴム組成物を加硫してなる[12]に記載のタイヤ用ゴム材料である。
1.マスターバッチ
1.1.ジエン系ゴム
1.2.親水性フュームドシリカ
1.3.シランカップリング剤
1.4.その他の成分
2.マスターバッチの製造方法
2.1.ニーダー
2.2.混練工程
3.タイヤ用ゴム組成物
4.タイヤ用ゴム組成物の製造方法
5.タイヤ用ゴム材料
本実施形態に係るマスターバッチは、ゴム材料を得るために用いられる混練物であり、ジエン系ゴム、親水性フュームドシリカおよびシランカップリング剤を含む。
本実施形態に係るマスターバッチに含まれるジエン系ゴムとしては、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレンブタジエンゴム、アクリロニトリルブタジエンゴム、ブチルゴム、エチレン-プロピレン-ジエンゴム、クロロプレンゴム等が例示される。これらの中でも、天然ゴムおよびイソプレンゴムから選ばれる少なくとも1つが好ましい。
フュームドシリカは、四塩化珪素を酸水素炎中で高温加水分解するによって製造される微粒子状の二酸化珪素である。したがって、フュームドシリカは、湿式シリカと製造方法が異なり、湿式シリカよりも一次凝集体(最小構成体)の一次粒子径が小さく、窒素吸着BET比表面積が大きい。フュームドシリカの粒子は、数珠状に凝集・融着しており、嵩高い凝集体を形成する。
シランカップリング剤がマスターバッチに含まれることにより、疎水性のジエン系ゴムと親水性フュームドシリカとの架橋構造がシランカップリング剤を介して形成されやすくなる。その結果、マスターバッチにおける親水性フュームドシリカの分散性を向上させ、タイヤ用ゴム材料の耐摩耗性を向上させることができる。
本実施形態では、マスターバッチは、上述した成分(ジエン系ゴム、親水性フュームドシリカおよびシランカップリング剤)以外に、ゴム組成物に配合される成分を含んでもよい。このような成分としては、たとえば、滑剤が例示される。マスターバッチが滑剤を含むことにより、マスターバッチの混練性が向上する。
図1に示すように、本実施形態に係るマスターバッチは、上述したジエン系ゴムと、上述した親水性フュームドシリカと、上述したシランカップリング剤と、必要に応じて、その他の成分と、を混練して得られる。
本実施形態では、ジエン系ゴムに対して、親水性フュームドシリカを十分練り込み、マスターバッチにおいて親水性フュームドシリカを十分分散させるために、ニーダーを用いて混練する。
混練工程では、上述したジエン系ゴムと、上述した親水性フュームドシリカと、上述したシランカップリング剤と、必要に応じてその他の成分と、をニーダーに投入して混練を行う。ローター回転数は上述したように20~40rpmである。また、混練物の温度が130~160℃の範囲内となるように冷却水量を調整することが好ましい。また、加圧式のニーダーの場合、混練時間は20~60分程度であることが好ましい。オープンニーダーの混練時間は、加圧式のニーダーの混練時間よりも長い方が好ましい。混練終了後、上記の成分が混練されたマスターバッチが得られる。このマスターバッチは、通常十分に練り込んで分散させることが困難である、嵩高い親水性フュームドシリカを高濃度で含むマスターバッチである。
本実施形態に係るタイヤ用ゴム組成物は、ジエン系ゴムと親水性フュームドシリカとシランカップリング剤とを含む。
図2に示すように、タイヤ用ゴム組成物は、好ましくは、上述したマスターバッチと、ジエン系ゴムと、必要に応じて、上述した成分と、を混練して得られる。すなわち、本実施形態では、タイヤ用ゴム組成物はマスターバッチに他の成分を配合して製造することが好ましい。また、マスターバッチに含まれるジエン系ゴムに加えて、さらにジエン系ゴムを配合する。一方、親水性フュームドシリカはマスターバッチに十分に含まれているので配合しない。
本実施形態に係るタイヤ用ゴム材料は、タイヤ用ゴム組成物が加硫処理されてなる材料である。
(マスターバッチの調製)
ジエン系ゴム100質量部に対する配合量が表1に示す配合量となるように、下記成分を容積が0.5Lの加圧ニーダーに投入した。投入後、ローター回転数が20~40rpmの範囲内で、混練物の温度が130~160℃の範囲内となるように30分間程度混練した。エアシリンダー圧は0.7MPaであった。混練終了後、室温まで冷却して、混練物を取り出しマスターバッチを得た。
(A)ジエン系ゴム
(A-1)ベトナム製天然ゴム:SVR
(B)充填剤
(B-1)親水性フュームドシリカ(トクヤマ製、レオロシールQS-30C、窒素吸着BET比表面積:300m2/g,タップ密度:100g/L)
(B-2)疎水性フュームドシリカ(トクヤマ製、レオロシールKS-30SC、窒素吸着BET比表面積:230m2/g,タップ密度:80g/L,M値:55)
(B-3)湿式シリカ(東ソーシリカ製、NipsilAQ、窒素吸着BET比表面積:200m2/g,タップ密度:300g/L)
(B-4)カーボンブラック(東海カーボン製、シースト6、窒素吸着BET比表面積:120m2/g,タップ密度:400g/L)
(C)シランカップリング剤
(C-1)メルカプト-チオカルボキシレートオリゴマー(Momentive製、NXT-Z45)
(C-2)ビス-(3-トリエトキシシリルプロピル)テトラサルファイド(Evonik製、Si69)
(D)その他の成分
(D-1)滑剤(ステアリン酸、日油製、ビーズステアリン酸YR)
(D-2)プロセスオイル(富士興産製、アロマックス3(TDAE Oil))
(D-3)プロセスオイル(1,3-プロパンジオール、富士フィルム和光純薬製)
得られたマスターバッチと(A-1)と下記に示す(D-4)および(D-5)とを、容積が1.7Lの密閉式バンバリーミキサーに投入した。投入後、ローター回転数が45~80rpmの範囲内で、混練物の温度が130~160℃の範囲内となるように10分間程混練した。混練中のラム圧力は0.5~4.0MPaの範囲内であった。混練終了後、室温まで冷却して、混練物を得た。
(D)その他の成分
(D-4)老化防止剤(精工化学製、オゾノン 6C)
(D-5)滑剤(酸化亜鉛、正同化学製、酸化亜鉛3種)
(D-6)硫黄(鶴見化学工業製、金華印油入微粉硫黄)
(D-7)加硫促進剤(N-(tert-ブチル)-2-ベンゾチアゾールスルフェンアミド(TBBS)、三新化学工業製、サンセラーNS-G)
得られたタイヤ用ゴム組成物の試験片について、ムーニー粘度計(上島製作所製VR-1132)を用いて、JIS K6300-1に準拠して、100℃におけるムーニー粘度(ML1+4 100℃)を測定した。ムーニー粘度が低いと、タイヤ用ゴム組成物の加工性が良好となる傾向にある。結果を表2に示す。
続いて、得られたタイヤ用ゴム組成物を150℃で10分間プレス加硫して、タイヤ用ゴム材料を得た。得られたタイヤ用ゴム材料から下記に示す評価を行うための試験片を作製した。得られた試験片を使用して、以下の物性を評価した。
得られたタイヤ用ゴム材料の試験片について、JIS K6253 タイプAに準拠して、デュロメータにより硬度(ショアA硬度)を測定した。タイヤ用ゴム材料の目標A硬度が65であるので、試験片のA硬度も65前後であることが好ましい。結果を表2に示す。
得られたタイヤ用ゴム材料の試験片について、JIS K6394に準拠して、動的粘弾性試験機(上島製作所製VR-7130)を用いて下記条件にて測定した。60℃における測定値からtanδ(60℃)を算出した。
静的歪 : 10%
動的歪 : ±2%
周波数 : 10Hz
算出された標準例1のtanδ(60℃)を1.0として下記計算式により転がり抵抗指数を算出した。指数が大きいほど転がり抵抗性に優れる。結果を表2に示す。
(転がり抵抗指数)=(標準例1のtanδ(60℃))/(実施例のtanδ(60℃))
得られたタイヤ用ゴム材料の試験片について、FPS摩耗試験機(上島製作所製AB-2012)を用いて、温度20℃、荷重40N、スリップ率10%、試験時間2分間の条件でFPS摩耗量を測定した。FPS摩耗量から容積損失を計算し、標準例1の損失量を1.0として下記計算式により摩耗指数を算出した。指数が大きいほど耐摩耗性能が優れる。結果を表2に示す。
(摩耗指数)=(標準例1の損失量)/(実施例の損失量)
架橋密度はトルエン膨潤法に基づき算出した。まず、タイヤ用ゴム材料の試験片を温度20℃のトルエンに48時間浸漬した。その後、得られたデータから、下記に示すFlory-Rehnerの式に基づき、充填剤は膨潤しないとした架橋密度を算出した。結果を表2に示す。
式中の「VR」は膨潤ゲル中のゴムのみの容積分率であり、下記の式から求められる。
VR=VP/(VP+VS)
「VP」は試験片中のゴムのみの容積であり、下記の式から求められる。
VP=(100W1)/(Z×d)
「W1」はゴム試験片重量である。「Z」は試験片中のゴム及び配合剤の重量比の合計であり、「d」はゴムの密度である。
「VS」は、試験片が吸収した溶媒容積であり、下記の式から求められる。
VS=(W2-W3)/ds
「W2」はトルエンで膨潤したゴム試験片の重量であり、「W3」はトルエンを乾燥除去後のゴム試験片の重量である。「ds」は溶媒(トルエン)の密度である。
「μ」はゴムと溶媒間の相互作用定数である。本実施例では、溶媒としてトルエンを用いたので、「μ」は0.39であった。
ジエン系ゴム100質量部に対する配合量が表3に示す配合量となるように、下記成分を容積が0.5Lの加圧ニーダーに投入した。投入後、ローター回転数が20~40rpmの範囲内で、混練物の温度が130~160℃の範囲内となるように30分間程度混練した。エアシリンダー圧は0.7MPaであった。混練終了後、室温まで冷却して、混練物を取り出しマスターバッチを得た。
(A)ジエン系ゴム
(A-1)ベトナム製天然ゴム:SVR
(B)充填剤
(B-1)親水性フュームドシリカ(トクヤマ製、レオロシールQS-30C、窒素吸着BET比表面積:300m2/g,タップ密度:100g/L)
(B-4)カーボンブラック(東海カーボン製、シースト6、窒素吸着BET比表面積:120m2/g,タップ密度:400g/L)
(C)シランカップリング剤
(C-1)メルカプト-チオカルボキシレートオリゴマー(Momentive製、NXT-Z45)
(D)その他の成分
(D-1)滑剤(ステアリン酸、日油製、ビーズステアリン酸YR)
(D-2)プロセスオイル(富士興産製、アロマックス3(TDAE Oil))
得られたマスターバッチと(A-1)と下記に示す(D-4)および(D-5)とを、容積が1.7Lの密閉式バンバリーミキサーに投入した。投入後、ローター回転数が45~80rpmの範囲内で、混練物の温度が130~160℃の範囲内となるように10分間程混練した。混練中のラム圧力は0.5~4.0MPaの範囲内であった。混練終了後、室温まで冷却して、混練物を得た。
(D)その他の成分
(D-4)老化防止剤(精工化学製、オゾノン 6C)
(D-5)滑剤(酸化亜鉛、正同化学製、酸化亜鉛3種)
(D-6)硫黄(鶴見化学工業製、金華印油入微粉硫黄)
(D-7)加硫促進剤(N-(tert-ブチル)-2-ベンゾチアゾールスルフェンアミド(TBBS)、三新化学工業製、サンセラーNS‐G)
続いて、得られたタイヤ用ゴム組成物を150℃で10分間プレス加硫して、タイヤ用ゴム材料を得た。得られたタイヤ用ゴム材料について、実験1と同じ評価を行うための試験片を作製した。得られた試験片を使用して、実験1において評価した物性(A硬度、低燃費性能、耐摩耗性、架橋密度)を評価した。結果を表4に示す。さらに、実験2では、標準例1および実施例1について耐熱老化性を以下のようにして評価した。
得られたタイヤ用ゴム組成物を厚さ2mmのモールドを用いて150℃で20分間加硫し、得られた加硫ゴムシートをJIS3号ダンベルで打ち抜きサンプルとした。サンプルを温度80℃に設定したギヤーオーブンで7日間(168時間)熱老化させた後、未老化のサンプルと共にJIS K625 1に従い引張試験機で破断伸びを測定した。未老化の破断伸び(Eb)と老化後の破断伸び(Ea)との比をとり、Ea/Ebを耐熱老化性の指標とした。算出した指標を用いて、標準例1の指標を1として下記計算式により耐熱指数を算出した。耐熱指数が大きいほど耐熱老化性に優れ、耐熱指数が105以下のとき、耐熱老化性が劣る。結果を表4に示す。
(耐熱指数)={(実施例の指標)/(標準例1の指標)}×100
ジエン系ゴム100質量部に対する配合量が表5に示す配合量となるように、下記成分を容積が0.5Lの加圧ニーダーに投入した。投入後、ローター回転数が20~40rpmの範囲内で、混練物の温度が130~160℃の範囲内となるように30分間程度混練した。エアシリンダー圧は0.7MPaであった。混練終了後、室温まで冷却して、混練物を取り出しタイヤ用ゴム組成物を得た。すなわち、実験3では、マスターバッチを用いずに、タイヤ用ゴム組成物を製造した。
(A)ジエン系ゴム
(A-1)ベトナム製天然ゴム:SVR
(B)充填剤
(B-1)親水性フュームドシリカ(トクヤマ製、レオロシールQS-30C、窒素吸着BET比表面積:300m2/g,タップ密度:100g/L)
(B-3)湿式シリカ(東ソーシリカ製、NipsilAQ、窒素吸着BET比表面積:200m2/g,タップ密度:300g/L)
(B-4)カーボンブラック(東海カーボン製、シースト6、窒素吸着BET比表面積:120m2/g,タップ密度:400g/L)
(B-5)親水性フュームドシリカ(トクヤマ製、レオロシールQS-10、窒素吸着BET比表面積:140m2/g,タップ密度:50g/L)
(B-6)親水性フュームドシリカ(トクヤマ製、レオロシールCP-102、窒素吸着BET比表面積:200m2/g,タップ密度:50g/L)
(B-7)親水性フュームドシリカ(トクヤマ製、レオロシールQS-40、窒素吸着BET比表面積:380m2/g,タップ密度:50g/L)
(B-8)親水性フュームドシリカ(トクヤマ製、試作品、窒素吸着BET比表面積:420m2/g,タップ密度:50g/L)
(B-9)親水性フュームドシリカ(トクヤマ製、試作品、窒素吸着BET比表面積:450m2/g,タップ密度:50g/L)
(C)シランカップリング剤
(C-1)メルカプト-チオカルボキシレートオリゴマー(Momentive製、NXT-Z45)
(D)その他の成分
(D-1)滑剤(ステアリン酸、日油製、ビーズステアリン酸YR)
(D-2)プロセスオイル(富士興産製、アロマックス3(TDAE Oil))
(D-4)老化防止剤(精工化学製、オゾノン 6C)
(D-5)滑剤(酸化亜鉛、正同化学製、酸化亜鉛3種)
(D-6)硫黄(鶴見化学工業製、金華印油入微粉硫黄)
(D-7)加硫促進剤(N-(tert-ブチル)-2-ベンゾチアゾールスルフェンアミド(TBBS)、三新化学工業製、サンセラーNS-G)
続いて、得られたタイヤ用ゴム組成物を150℃で10分間プレス加硫して、タイヤ用ゴム材料を得た。得られたタイヤ用ゴム材料について、実験1と同じ評価を行うための試験片を作製した。得られた試験片を使用して、実験1において評価した物性(A硬度、低燃費性能、耐摩耗性、架橋密度)を評価した。
Claims (13)
- ジエン系ゴム100質量部に対して、親水性フュームドシリカを13質量部以上130質量部以下、シランカップリング剤を1質量部以上40質量部以下含むマスターバッチ。
- 前記親水性フュームドシリカのBET比表面積が50m2/g以上500m2/g以下である請求項1に記載のマスターバッチ。
- 前記ジエン系ゴムが、天然ゴムおよびイソプレンゴムからなる群から選ばれる少なくとも1つである請求項1または2に記載のマスターバッチ。
- ジエン系ゴム100質量部に対して、滑剤を1質量部以上40質量部以下含む請求項1から3のいずれかに記載のマスターバッチ。
- ニーダーを用いて、ジエン系ゴムと親水性フュームドシリカとシランカップリング剤とを混練する工程を有するマスターバッチの製造方法。
- 前記親水性フュームドシリカのBET比表面積が50m2/g以上500m2/g以下である請求項5に記載のマスターバッチの製造方法。
- さらに、滑剤を混錬する請求項5または6に記載のマスターバッチの製造方法。
- ジエン系ゴム100質量部に対して、親水性フュームドシリカを5質量部以上90質量部以下、シランカップリング剤を1.5質量部以上30質量部以下含むタイヤ用ゴム組成物。
- 前記親水性フュームドシリカのBET比表面積が50m2/g以上500m2/g以下である請求項8に記載のタイヤ用ゴム組成物。
- 請求項1から4のいずれかに記載のマスターバッチを含む請求項8に記載のタイヤ用ゴム組成物。
- 請求項1から4のいずれかに記載のマスターバッチと、ジエン系ゴムと、を混練する工程を有するタイヤ用ゴム組成物の製造方法。
- A硬度が55~72であり、トルエン膨潤法に基づく架橋密度が4×10-5mol/mL以上27.5×10-5mol/mL未満であるタイヤ用ゴム材料。
- 請求項8から10のいずれかに記載のタイヤ用ゴム組成物を加硫してなる請求項12に記載のタイヤ用ゴム材料。
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WO2024085031A1 (ja) * | 2022-10-18 | 2024-04-25 | 株式会社トクヤマ | マスターバッチ、マスターバッチの製造方法、タイヤ用ゴム組成物、タイヤ用ゴム組成物の製造方法、タイヤ用ゴム材料およびタイヤ |
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WO2024085031A1 (ja) * | 2022-10-18 | 2024-04-25 | 株式会社トクヤマ | マスターバッチ、マスターバッチの製造方法、タイヤ用ゴム組成物、タイヤ用ゴム組成物の製造方法、タイヤ用ゴム材料およびタイヤ |
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