WO2012147976A1 - ゴム組成物 - Google Patents
ゴム組成物 Download PDFInfo
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- WO2012147976A1 WO2012147976A1 PCT/JP2012/061490 JP2012061490W WO2012147976A1 WO 2012147976 A1 WO2012147976 A1 WO 2012147976A1 JP 2012061490 W JP2012061490 W JP 2012061490W WO 2012147976 A1 WO2012147976 A1 WO 2012147976A1
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- 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
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Definitions
- the present invention relates to a rubber composition containing silica that improves low heat build-up.
- silica is aggregated in the rubber composition (because of aggregation due to hydroxyl groups on the silica surface), a silane coupling agent is used to prevent aggregation. Therefore, various attempts have been made in order to improve the activity of the coupling function of the silane coupling agent in order to suitably solve the above problems by blending the silane coupling agent.
- Patent Document 1 at least (i) one diene elastomer as a basic component, (ii) a white filler as a reinforcing filler, and (iii) a polysulfide as a coupling agent (white filler / diene elastomer). Rubber compositions containing alkoxysilanes together with (iv) enamines and (v) guanidine derivatives have been proposed.
- Patent Document 2 as a basic component, at least (i) one diene elastomer, (ii) a white filler as a reinforcing filler, and (iii) a polysulfide as a coupling agent (white filler / diene elastomer).
- a rubber composition comprising an alkoxysilane together with (iv) zinc dithiophosphate and (v) a guanidine derivative is disclosed.
- Patent Document 3 is based on at least (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler, and (iii) a polysulfated alkoxysilane (PSAS) as a (inorganic filler / diene elastomer) coupling agent. And (iv) a rubber composition in which aldimine (R—CH ⁇ N—R) and (v) a guanidine derivative are used in combination.
- PSAS polysulfated alkoxysilane
- Patent Document 4 based on at least: (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler, (iii) a polysulfated alkoxysilane as a coupling agent, (iv) 1,2-dihydropyridine and ( v) Rubber compositions with guanidine derivatives have been proposed.
- Patent Document 5 a technique for enhancing the activity of the coupling function of the silane coupling agent in consideration of the kneading conditions is also proposed.
- Patent Document 6 discloses an invention in which silica having an average particle size of 10 ⁇ m or less and a specific silane coupling agent are blended with a rubber composition to suppress silica aggregation.
- a rubber composition is blended with a tea extract containing silica and catechin having an adsorption specific surface area of n-hexadecyltrimethylammonium bromide (CTAB) of preferably 60 to 250 ⁇ 10 2 m 2 / kg.
- CTAB n-hexadecyltrimethylammonium bromide
- Patent Documents 8 and 9 in the dispersion evaluation method in which the dispersion state of the filler contained in the rubber component observes the cut surface of the sample by the dark field method, the equivalent circle diameter with respect to the entire observation visual field area.
- a rubber composition is disclosed in which a ratio of an area occupied by a filler aggregate of 10 ⁇ m or more is 2.0% or less,
- there is a demand for a technique for further improving the low heat build-up in a rubber composition containing silica there is a demand for a technique for further improving the low heat build-up in a rubber composition containing silica.
- An object of the present invention is to provide a rubber composition having improved low heat buildup under such circumstances.
- the present inventors have focused on the dispersion state of silica in the rubber composition and attempted to evaluate the dispersion state of silica by various measurement methods. As a result, it has been found that if the average aggregate aggregate area by a specific measurement method is set to a specific value or less, the hysteresis characteristics (particularly, tan ⁇ ) of the rubber composition can be reduced and the low heat build-up can be improved. It came to complete. That is, the present invention relates to a rubber component (A) comprising at least 10% by mass of at least one rubber selected from diene rubbers and natural rubbers synthesized by emulsion polymerization and 90% by mass or less of other diene rubbers, ASTM D3765.
- the average aggregate aggregate area of the silica portion per unit area (3 ⁇ m ⁇ 3 ⁇ m) is calculated by number average (arithmetic average). In the calculation, particles in contact with the edge (side) of the image are not counted, and particles of 20 pixels or less are regarded as noise and are not counted.
- FIG. 4 is a photograph showing an example of a FIB-SEM image obtained by photographing the aggregate aggregate of silica in the rubber composition of the present invention by the method for measuring the average aggregate aggregate area according to the present invention. It is a photograph which shows an example of the binarized image of the image shown in FIG.
- FIG. 6 is a photograph showing another reference example of the FIB-SEM image obtained by photographing the aggregated aggregate of silica by the same method as FIG. It is a photograph which shows an example of the binarized image of the image shown in FIG.
- the rubber composition of the present invention comprises a rubber component (A) comprising 10% by mass or more of at least one rubber selected from diene rubbers and natural rubbers synthesized by emulsion polymerization and 90% by mass or less of other diene rubbers, Silica (B) having a n-hexadecyltrimethylammonium bromide (CTAB) adsorption specific surface area of 140 m 2 / g or more and less than 180 m 2 / g measured according to the method described in ASTM D3765-92, and a polysulfide compound, A rubber composition comprising a silane coupling agent (C) selected from at least one thioester compound and a vulcanization accelerator (D), the average aggregate aggregate area of the silica of the rubber composition after vulcanization ( nm 2 ) is 2300 or less.
- a rubber component (A) comprising 10% by mass or more of at least one rubber selected from diene rubbers and natural rubbers synthesized by emul
- the average aggregate aggregate area (nm 2 ) of the silica is preferably 2200 or less, and more preferably 2150 or less.
- the average aggregate aggregate area (nm 2 ) of the silica is preferably 300 or more, more preferably 300 to 2300, further preferably 300 to 2200, and particularly preferably 300 to 2150.
- the average aggregate aggregate area is measured by cutting the upper surface of the vulcanized rubber composition sample using a focused ion beam in a direction that forms an angle of 38 ° with the upper surface of the sample.
- the smooth surface of the sample formed by the above is photographed at an acceleration voltage of 5 kV using a scanning electron microscope from a direction perpendicular to the smooth surface.
- the aggregated aggregate area of the silica part is obtained.
- the average aggregate aggregate area of the silica part per unit area (3 ⁇ m ⁇ 3 ⁇ m) is calculated by number average (arithmetic mean). However, in the calculation, particles in contact with the edge (side) of the image are not counted, and particles of 20 pixels or less are not counted as noise.
- FIB-SEM In measuring the average aggregate aggregate area according to the present invention, it is preferable to use a FIB-SEM in which a focused ion beam processing observation apparatus (FIB) and a scanning electron microscope (SEM) are combined into one apparatus. Moreover, it is preferable to use a very low acceleration voltage scanning electron microscope as a scanning electron microscope (SEM). Examples of the FIB-SEM include a product name “NOVA200” (registered trademark), a product name “SMI-3050MS2” (registered trademark) manufactured by FEI, and a product name “SMI-3050MS2” (registered trademark). NOVA200 "(registered trademark) is preferred.
- An image processing apparatus based on the Otsu method is used for conversion to a binary image.
- the top surface of the rubber composition sample after vulcanization is cut using a focused ion beam in a direction that forms an angle of 38 ° with respect to the top surface of the sample.
- the smooth surface of the sample formed by the above is photographed at an acceleration voltage of 5 kV using a scanning electron microscope from a direction perpendicular to the smooth surface.
- a high-accuracy image including only the surface information of the cross section can be obtained for a flat cross section of the sample without being affected by the difference in brightness or the focus shift.
- the dispersion state of the filler in the polymer material is quantified, and the average aggregate aggregate area of the vulcanized rubber composition containing silica is quantitatively evaluated. It became possible.
- the cut surface formed in the direction parallel to the FIB irradiation direction is a smooth surface without unevenness, and the cutting surface formed in the direction perpendicular to the FIB irradiation direction is rough surface with unevenness. It becomes.
- the smooth surface used for photographing in the present invention means a cutting surface formed in a direction parallel to the FIB irradiation direction.
- a threshold value for binarization of the obtained image is determined using the Otsu method. Based on the binarized image obtained by converting the rubber portion of the sample and the silica portion serving as the filler, the aggregated aggregate area of the silica portion is obtained, and the total surface area of the silica portion is calculated. From the number of aggregates, the average aggregate aggregate area of the silica portion per unit area (3 ⁇ m ⁇ 3 ⁇ m) is calculated by number average (arithmetic average). In the calculation, particles in contact with the edge (side) of the image are not counted, and particles of 20 pixels or less are regarded as noise and are not counted.
- FIG. 1 is a photograph showing an example of a FIB-SEM image obtained by photographing the aggregate aggregate of silica in the rubber composition of the present invention by the method for measuring the average aggregate aggregate area according to the present invention. It is a photograph which shows an example of the binarized image of the image shown in FIG. 3 is a photograph showing another reference example of the FIB-SEM image obtained by photographing the aggregated aggregate of silica by the same method as FIG. 1, and FIG. 4 is a binary image of the image shown in FIG. It is a photograph which shows an example.
- the aggregate aggregate in the present invention refers to an aggregate of a plurality of aggregates, and includes a single aggregate.
- the aggregate primary aggregate
- the aggregate is a complex aggregate form in which the basic particles of silica are fused and branched into a chain or irregular chain, and several tens to several hundreds of nanometers.
- the size of Aggregate aggregates in the present invention are much smaller than agglomerates (secondary aggregates) that are usually considered to be tens to hundreds of microns in size, and they are completely different concepts.
- CTAB adsorption specific surface area (hereinafter abbreviated as “CTAB adsorption specific surface area”) of silica is based on the method described in ASTM D3765-92. Measured. However, since the method described in ASTM D3765-92 is a method for measuring the CTAB adsorption specific surface area of carbon black, it was slightly modified. In other words, a standard n-hexadecyltrimethylammonium bromide (CTAB) standard solution was prepared without using IRB # 3 (83.0 m 2 / g), which is a standard product of carbon black.
- IRB # 3 83.0 m 2 / g
- the rubber component (A) used in the rubber composition of the present invention is at least 10% by mass of at least one rubber selected from diene rubbers and natural rubbers synthesized by emulsion polymerization and 90% by mass or less of other diene rubbers. However, it is preferable that it exceeds 10% by mass of at least one rubber selected from diene rubber synthesized by emulsion polymerization and natural rubber and less than 90% by mass of other diene rubber.
- the diene rubber synthesized by emulsion polymerization according to the present invention may be synthesized using a normal emulsion polymerization technique. For example, a method in which a predetermined amount of the following monomer is emulsified and dispersed in an aqueous medium in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator.
- a emulsifier for example, a long-chain fatty acid salt and / or rosinate having 10 or more carbon atoms is used. Specific examples include potassium salts such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and sodium salts.
- radical polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate; a combination of ammonium persulfate and ferric sulfate; a combination of organic peroxide and ferric sulfate; Redox initiators such as a combination of hydrogen oxide and ferric sulfate are used.
- a chain transfer agent may be added to adjust the molecular weight of the diene rubber.
- chain transfer agent for example, mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan, ⁇ -methylstyrene dimer, carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, ⁇ -terbinene and the like can be used.
- the temperature of the emulsion polymerization can be appropriately selected depending on the type of radical polymerization initiator used, but is usually 0 to 100 ° C., preferably 0 to 60 ° C.
- the polymerization mode may be either continuous polymerization or batch polymerization.
- the polymerization conversion rate is preferably suppressed to 90% or less, and in particular, the polymerization is preferably stopped in the range of the conversion rate of 50 to 80%.
- the termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined conversion rate is reached.
- the polymerization terminator include amine compounds such as diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, sodium nitrite, and sodium dithiocarbamate.
- Examples of the conjugated diene used in the diene rubber synthesized by emulsion polymerization according to the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl- Examples thereof include 1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene and the like. Among these, 1,3-butadiene, 2-methyl-1,3-butadiene and the like are preferable, and 1,3-butadiene is more preferable.
- These conjugated dienes can be used alone or in combination of two or more.
- aromatic vinyl examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert- Examples thereof include butyl styrene and 5-tert-butyl-2-methyl styrene. Among these, styrene is preferable. These aromatic vinyls are used alone or in combination of two or more.
- the diene rubber synthesized by emulsion polymerization according to the present invention is preferably a styrene-butadiene copolymer rubber (hereinafter sometimes referred to as “emulsion polymerization SBR”).
- emulsion polymerization SBR styrene-butadiene copolymer rubber
- the styrene component is preferably contained in the range of 5 to 50% by mass, more preferably in the range of 10 to 50% by mass, and further preferably in the range of 15 to 45% by mass. preferable.
- diene rubbers in the rubber component (A) used in the rubber composition of the present invention include solution polymerized styrene-butadiene copolymer rubber (hereinafter sometimes referred to as “solution polymerized SBR”), polybutadiene rubber. (Hereinafter sometimes referred to as “BR”) and at least one rubber selected from synthetic polyisoprene rubber (hereinafter sometimes referred to as “IR”) is preferred.
- solution polymerized SBR solution polymerized styrene-butadiene copolymer rubber
- BR polybutadiene rubber
- IR synthetic polyisoprene rubber
- the solution-polymerized SBR includes an unmodified styrene-butadiene copolymer rubber (hereinafter sometimes referred to as “unmodified solution-polymerized SBR”) and / or a modified styrene-butadiene copolymer having a molecular chain end modified with a tin compound.
- a combined rubber hereinafter sometimes referred to as “tin-modified solution polymerization SBR” is preferable.
- tin-modified solution polymerization SBR is preferable.
- These other diene rubbers may be used alone or as a blend of two or more.
- the unmodified solution polymerization SBR is obtained by anionic polymerization or coordination polymerization, but is preferably produced by anionic polymerization.
- the polymerization initiator used for the anionic polymerization is an alkali metal compound, but a lithium compound is preferable.
- the lithium compound not only a normal lithium compound (particularly hydrocarbyl lithium or lithium amide compound), but also a tin compound having a tin atom (for example, tributyltin lithium, trioctyltin lithium, etc.) when obtaining tin-modified solution polymerization SBR May also be used.
- Tin-modified solution polymerization SBR reacts with a tin compound as a modifier on the polymerization active terminal of the styrene-butadiene copolymer after completion of the polymerization reaction of the unmodified solution polymerization SBR obtained as described above, and before the termination of the polymerization. Is obtained.
- the tin compound include tin tetrachloride, tributyltin chloride, trioctyltin chloride, dioctyltin dichloride, dibutyltin dichloride, and triphenyltin chloride.
- silica (B) As the silica (B) used in the rubber composition of the present invention, any commercially available one can be used. Among them, wet silica, dry silica and colloidal silica are preferably used, and wet silica is more preferably used. Wet silica is classified into precipitated silica and gel silica. Precipitated silica is particularly preferable because it is easily dispersed in the rubber composition by kneading shear and has excellent reinforcing properties due to surface reaction after dispersion. Moreover, the CTAB adsorption specific surface area of silica (B) is 140 m 2 / g or more and less than 180 m 2 / g.
- CTAB adsorption specific surface area 160 m 2 / g
- the rubber composition of the present invention may contain carbon black in addition to the above silica (B) if desired.
- carbon black is not particularly limited.
- high, medium or low structure SAF, ISAF, IISAF, N339, HAF, FEF, GPF, SRF grade carbon black, particularly SAF, ISAF, IISAF, N339, HAF, Preferably, FEF grade carbon black is used.
- the nitrogen adsorption specific surface area (N 2 SA, measured according to JIS K 6217-2: 2001) is preferably 30 to 250 m 2 / g. This carbon black may be used individually by 1 type, and may be used in combination of 2 or more type.
- the rubber composition of the present invention preferably contains 25 to 150 parts by mass of silica (B) with respect to 100 parts by mass of the rubber component (A). If it is 25 mass parts or more, it is preferable from a viewpoint of ensuring wet performance, and if it is 150 mass parts or less, it is preferable from a viewpoint of rolling resistance reduction. Furthermore, it is more preferable to contain 25 to 120 parts by mass of silica (B), and it is more preferable to contain 30 to 85 parts by mass of silica (B).
- the rubber composition of the present invention preferably contains 25 to 170 parts by mass of a filler composed of silica (B) and optionally added carbon black with respect to 100 parts by mass of the rubber component (A).
- silica (B) is preferably 40% by mass or more from the viewpoint of achieving both wet performance and rolling resistance, and more preferably 70% by mass or more.
- the silane coupling agent (C) used in the rubber composition of the present invention is required to be a silane coupling agent selected from at least one selected from a polysulfide compound and a thioester compound. Polysulfide compounds and thioester compounds are preferred because they do not cause scorching during kneading and can improve processability.
- the silane coupling agent (C) selected from at least one selected from polysulfide compounds and thioester compounds is preferably a compound selected from the group consisting of compounds represented by the following general formulas (I) to (IV). .
- the rubber composition according to the method of the present invention is further excellent in workability during rubber processing and can provide a pneumatic tire with better wear resistance. it can.
- a preferred example of the polysulfide compound is a compound represented by the following general formula (I) or (III)
- a preferred example of the thioester compound is a compound represented by the following general formula (II) or (IV).
- the following general formulas (I) to (IV) will be described in order.
- R 1 s may be the same or different and are each a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms
- R 2 May be the same or different, each having 1 to 8 carbon straight, cyclic or branched alkyl groups
- R 3 may be the same or different, each having 1 to 8 carbon straight or branched
- a is an average value of 2 to 6
- p and r may be the same or different, and each has an average value of 0 to 3, provided that both p and r are not 3.
- silane coupling agent (C) represented by the general formula (I) include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (3-methyl Dimethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) Disulfide, bis (2-triethoxysilylethyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-methyldimethoxysilylpropyl) trisulfide Bis (2-trieth
- R 9 , R 10 and R 11 may be the same or different and each is a hydrogen atom or 1 to 18 is a monovalent hydrocarbon group having an average value of 1 to 4)
- R 5 is R 4 , a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms
- R 6 Is R 4 , R 5 a hydrogen atom or a — [O (R 12 O) j ] 0.5 — group
- R 12 is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4
- R 7 Represents a divalent hydrocarbon group having 1 to 18 carbon atoms
- R 8 represents a monovalent hydrocarbon
- R 8 , R 9 , R 10 and R 11 may be the same or different and are preferably each a linear, cyclic or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. And a group selected from the group consisting of an aryl group and an aralkyl group.
- R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, it is a group selected from the group consisting of a linear, cyclic or branched alkyl group, alkenyl group, aryl group and aralkyl group.
- R 12 is preferably a linear, cyclic or branched alkylene group, particularly preferably a linear one.
- R 7 is, for example, an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, a cycloalkylalkylene group having 6 to 18 carbon atoms, or an arylene having 6 to 18 carbon atoms. And an aralkylene group having 7 to 18 carbon atoms.
- the alkylene group and alkenylene group may be linear or branched, and the cycloalkylene group, cycloalkylalkylene group, arylene group, and aralkylene group may have a substituent such as a lower alkyl group on the ring. You may have.
- R 7 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group. it can.
- Specific examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms of R 5 , R 8 , R 9 , R 10 and R 11 in the general formula (II) include a methyl group, an ethyl group, and an n-propyl group.
- R 12 in the general formula (II) examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group and the like.
- silane coupling agent (C) represented by the general formula (II) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltri Ethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysi
- R 13 may be the same or different and each is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms
- R 14 May be the same or different, each having a straight chain, cyclic or branched alkyl group having 1 to 8 carbon atoms
- R 15 may be the same or different, each having a straight chain or branched structure having 1 to 8 carbon atoms.
- R 16 is an alkylene group of the general formula (—S—R 17 —S—), (—R 18 —S m1 —R 19 —) and (—R 20 —S m2 —R 21 —S m3 —R 22 —).
- Any one of divalent groups (R 17 to R 22 may be the same or different and each is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, or other than sulfur and oxygen) It is a divalent organic group containing a hetero element, and m1, m2, and m3 may be the same or different and each has an average value of 1 or more Less than 4), k may be the same or different and each is an average value of 1 to 6, and s and t may be the same or different, and each is an average value of 0 to 3, provided that Both s and t are not 3.
- silane coupling agent (C) represented by the general formula (III), Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 2 — (CH 2 ) 6 —S 2 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 2 — (CH 2 ) 10 —S 2 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 3 — (CH 2 ) 6 —S 3 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 4 — (CH 2 ) 6 —S 4 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 ,
- R 23 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms
- G may be the same or different, and each is an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms
- Z a may be the same or different, each being a group capable of bonding to two silicon atoms, and [ ⁇ 0 ⁇ ] 0.5 , [ ⁇ 0 ⁇ G ⁇ ] 0.5 or [—O—G—O— ]
- a group selected from 0.5 , Z b may be the same or different, each being a group capable of bonding to two silicon atoms, and a functional group represented by [—O—G—O—] 0.5
- Z c may be the same or different and each represents —Cl, —Br, —OR a , R a C ( ⁇ O) O—, R a R b C ⁇ NO—, R a R b N -, R a -, HO- G-O- (.
- R a and R b are good be the same or different Are each straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms.
- each of Z a u , Z b v and Z c w in the plurality of A parts may be the same or different.
- Z a in a plurality of B parts Each of u , Z b v and Z c w may be the same or different.
- silane coupling agent (C) represented by the general formula (IV) include chemical formula (V), chemical formula (VI), and chemical formula (VII).
- silane coupling agent represented by the chemical formula (V) [trade name “NXT Low-V Silane” (registered trademark)] manufactured by Momentive Performance Materials Inc. is commercially available.
- silane coupling agent represented by the chemical formula (VI) [Momentive Performance Materials Inc., trade name “NXT Ultra Low-V Silane” (registered trademark)] can be obtained as a commercial product. it can.
- examples of the silane coupling agent represented by the chemical formula (VII) include a product name “NXT-Z” (registered trademark) manufactured by Momentive Performance Materials Inc.
- silane coupling agent obtained by the above general formula (II), chemical formula (V) and chemical formula (VI) has a protected mercapto group, initial vulcanization (scorch) during processing in the process prior to the vulcanization process. ) Can be prevented, so that workability is improved.
- the silane coupling agent obtained by chemical formula (V), (VI) and (VII) has many alkoxysilane carbon number, there is little generation
- the silane coupling agent (C) according to the present invention is particularly preferably a compound represented by the above general formula (I) among the compounds represented by the above general formulas (I) to (IV).
- a silane coupling agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the blending amount of the silane coupling agent (C) in the rubber composition of the present invention is preferably 1 to 20% by mass of silica. If the amount is less than 1% by mass, the effect of improving the low heat build-up of the rubber composition is difficult to be exhibited. Further, it is more preferably 3 to 20% by mass of silica, and particularly preferably 4 to 10% by mass of silica.
- the production method of the rubber composition is not limited and may be produced by any kneading method. However, the following production methods (1) to (5) However, it is preferable from the viewpoint of being able to produce with normal equipment and high productivity.
- the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), silica (B), all or part of the silane coupling agent (C), and vulcanization.
- a rubber composition in which the accelerator (D) is added and kneaded, and the molar amount of the organic acid compound in the rubber composition in the first stage is limited to 1.5 times or less the molar amount of the vulcanization accelerator (D).
- the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides and thiazoles.
- the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), silica (B), and all or part of the silane coupling agent (C).
- a method for producing a rubber composition which is kneaded and then kneaded by adding a vulcanization accelerator (D) during the first stage.
- the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
- the rubber composition is kneaded in three or more kneading stages, and in the first kneading stage (X), all or part of the rubber component (A), silica (B), and silane coupling agent (C) All or a part of the mixture is kneaded, and after the second stage of kneading and before the final stage (Y), the vulcanization accelerator (D) is added and kneaded, and vulcanized in the final stage (Z) of kneading.
- the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
- the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), silica (B), and all or part of the silane coupling agent (C), And a method for producing a rubber composition in which the vulcanization accelerator (D) is kneaded.
- the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
- the following (5) is desirable.
- the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), silica (B), all or part of the silane coupling agent (C), and the addition
- a rubber which is kneaded by adding a sulfur accelerator (D) and restricts the molar amount of the organic acid compound in the rubber composition in the first stage to 1.5 times or less the molar amount of the sulfur accelerator (D).
- a method for producing the composition is kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), silica (B), all or part of the silane coupling agent (C), and the addition
- a rubber which is kneaded by adding a sulfur accelerator (D) and restricts the molar amount of the organic acid compound in the rubber composition in the first stage to 1.5 times or less the molar amount of the sulfur accelerator (D).
- the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
- the kneading stage before the final stage such as the first stage and the second stage refers to chemicals related to crosslinking, such as rubber components, fillers, and coupling agents ( This is a step of blending and kneading raw materials other than vulcanizing agents and vulcanization accelerators, and is a step for reinforcing the rubber component by dispersing the filler into the rubber composition.
- a kneading process in which only the kneading is performed without adding the raw materials is not included, and a special mixing method such as a wet masterbatch is not included.
- the maximum temperature of the rubber composition in the kneading stage prior to the final stage such as the first stage and the second stage is preferably 120 to 190 ° C, more preferably 130 to 175 ° C, and 150 to 170 ° C. More preferably it is.
- the kneading time is preferably from 0.5 minutes to 20 minutes, more preferably from 0.5 minutes to 10 minutes, and further preferably from 0.5 minutes to 5 minutes.
- the final stage of kneading refers to a step of blending and kneading chemicals related to crosslinking (vulcanizing agent, vulcanization accelerator).
- the maximum temperature of the rubber composition in this final stage is preferably 60 to 140 ° C, more preferably 80 to 120 ° C, and further preferably 100 to 120 ° C.
- the kneading time is preferably from 0.5 minutes to 20 minutes, more preferably from 0.5 minutes to 10 minutes, and further preferably from 0.5 minutes to 5 minutes.
- Vulcanization accelerator (D) Preferred examples of the vulcanization accelerator (D) used in the rubber composition of the present invention include guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
- guanidine used in the rubber composition of the present invention include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salt of dicatechol borate.
- 1,3-di-o-cumenyl guanidine, 1,3-di-o-biphenyl guanidine, 1,3-di-o-cumenyl-2-propionyl guanidine, and the like can be mentioned.
- 1,3-diphenyl guanidine, 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide are preferred because of their high reactivity.
- Examples of the sulfenamide used in the rubber composition of the present invention include N-cyclohexyl-2-benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothiazolylsulfenamide, N-tert-butyl- 2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-methyl-2-benzothiazolylsulfenamide, N-ethyl-2-benzothiazolylsulfenamide, N -Propyl-2-benzothiazolylsulfenamide, N-butyl-2-benzothiazolylsulfenamide, N-pentyl-2-benzothiazolylsulfenamide, N-hexyl-2-benzothiazolylsulfenamide N-pentyl-2-benzothiazolylsulfenamide, N-octy -2-Benz
- Examples of thiazoles used in the rubber composition of the present invention include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2 -(N, N-diethylthiocarbamoylthio) benzothiazole, 2- (4'-morpholinodithio) benzothiazole, 4-methyl-2-mercaptobenzothiazole, di- (4-methyl-2-benzothiazolyl) disulfide, 5 -Chloro-2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, 2-mercapto-6-nitrobenzothiazole, 2-mercapto-naphtho [1,2-d] thiazole, 2-mercapto-5-methoxybenzothiazole, 6-amino-2-me Mercaptobenzothiazole, and the like. Of these, 2-mercapto
- Thiurams used in the rubber composition of the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptyl Thiuram disulfide, tetraoctyl thiuram disulfide, tetranonyl thiuram disulfide, tetradecyl thiuram disulfide, tetradodecyl thiuram disulfide, tetrastearyl thiuram disulfide, tetrabenzyl thiuram disulfide, tetrakis (2-ethylhexyl)
- dithiocarbamate used in the rubber composition of the present invention examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc diisopropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, and zinc dihexyldithiocarbamate.
- zinc dibenzyldithiocarbamate zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate are preferred because of their high reactivity.
- thioureas used in the rubber composition of the present invention include N, N′-diphenylthiourea, trimethylthiourea, N, N′-diethylthiourea, N, N′-dimethylthiourea, and N, N′-dibutylthiourea.
- Ethylenethiourea N, N'-diisopropylthiourea, N, N'-dicyclohexylthiourea, 1,3-di (o-tolyl) thiourea, 1,3-di (p-tolyl) thiourea, 1, 1-diphenyl-2-thiourea, 2,5-dithiobiurea, guanylthiourea, 1- (1-naphthyl) -2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, o-tolylthiourea Etc.
- N, N'-diethylthiourea, trimethylthiourea, N, N'-diphenylthiourea and N, N'-dimethylthiourea are preferred because of their high reactivity.
- Examples of xanthates used in the rubber composition of the present invention include zinc methylxanthate, zinc ethylxanthate, zinc propylxanthate, zinc isopropylxanthate, zinc butylxanthate, zinc pentylxanthate, zinc hexylxanthate, Zinc heptylxanthate, zinc octylxanthate, zinc 2-ethylhexylxanthate, zinc decylxanthate, zinc dodecylxanthate, potassium methylxanthate, potassium ethylxanthate, potassium propylxanthate, potassium isopropylxanthate, butylxanthate Potassium, potassium pentylxanthate, potassium hexylxanthate, potassium heptylxanthate, octyl chloride Potassium tonate, potassium 2-ethylhexyl
- the rubber composition of the present invention preferably contains 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass of the vulcanization accelerator (D) with respect to 100 parts by mass of the rubber component (A). More preferably. Among these, it is preferable to add 0.1 to 5 parts by mass of the vulcanization accelerator (D) before the final stage of kneading, and it is preferable to add 0.1 to 5 parts by mass at the final stage of kneading. .
- Organic acid compound examples include stearic acid, palmitic acid, myristic acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, capric acid, pelargonic acid, caprylic acid, enanthic acid, capron Organic acids selected from saturated fatty acids such as acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, nervonic acid and unsaturated fatty acids, and resin acids such as rosin acid and modified rosin acid, metal salts or esters of the above organic acids And phenol derivatives.
- 50 mol% or more in the organic acid compound is preferably stearic acid because it is necessary to sufficiently exhibit the function as a vulcanization acceleration aid.
- various compounding agents such as a vulcanization activator such as zinc white and an anti-aging agent blended in the rubber composition are mixed in the first stage or the final stage of kneading, if necessary. It is kneaded in an intermediate stage between the first stage and the final stage.
- a Banbury mixer, a roll, an intensive mixer or the like is used as the kneading apparatus in the present invention.
- the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
- the average aggregation aggregate area and low exothermic property (tan ⁇ index) of the vulcanized rubber composition were evaluated by the following methods.
- a rubber composition sample after vulcanization was prepared by cutting a vulcanized rubber sheet with a razor.
- the shape was 5 mm ⁇ 5 mm ⁇ thickness 1 mm.
- FIB-SEM manufactured by FEI, NOVA200
- the upper surface of the sample was cut in a direction forming an angle of 38 ° with respect to the upper surface of the sample using a focused ion beam under the condition of a voltage of 30 kV.
- the smooth surface of the sample formed by cutting was photographed at an acceleration voltage of 5 kV using a SEM from a direction perpendicular to the smooth surface.
- the aggregated aggregate area of the silica part is obtained. From the total surface area of the silica part and the number of aggregates, the average aggregate aggregate area of the silica part per unit area (3 ⁇ m ⁇ 3 ⁇ m) was calculated by number average (arithmetic mean). In the calculation, particles in contact with the edge (side) of the image were not counted, and particles of 20 pixels or less were regarded as noise and were not counted.
- Emulsion polymerization SBR-1 Emulsion polymerization styrene-butadiene copolymer rubber (SBR) manufactured by JSR Corporation, trade name “# 1500”
- Solution polymerization SBR-2 Asahi Kasei Corporation, unmodified solution polymerization styrene-butadiene copolymer rubber (SBR), trade name “Toughden 2000”
- Natural rubber RSS # 3 (4) Carbon Black N220: Asahi Carbon Co., Ltd., trade name “# 80”
- Example 1 In the first stage of kneading, 25 parts by mass of emulsion polymerization SBR-1 and 75 parts by mass of solution polymerization SBR-2, 10 parts by mass of carbon black N220, silica (B) as a rubber component (A) in a Banbury mixer. 50 parts by mass of silica-1, 4 parts by mass of silane coupling agent Si75 as silane coupling agent (C) and 30 parts by mass of aromatic oil were kneaded for 60 seconds, and then vulcanization accelerator (D) was used.
- Example 2 Kneading was carried out in the same manner as in Example 1 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Example 3 Kneading was carried out in the same manner as in Example 1 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Example 4 Kneading was carried out in the same manner as in Example 1 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A) and that the maximum temperature of the rubber composition in the first stage of kneading was adjusted to 170 ° C.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Comparative Example 1 In the first stage of kneading, 1 part by weight of 1,3-diphenylguanidine is not added, and in the final stage of kneading, neither 2 parts by weight of stearic acid or 1 part by weight of anti-aging agent 6PPD is added. Kneaded in the same manner as in Example 1 except that 100 parts by mass of solution-polymerized SBR-2 was used as the rubber component (A) in the stage, and 2 parts by mass of stearic acid and 1 part by mass of anti-aging agent 6PPD were added. . The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Comparative Example 2 Kneading was carried out in the same manner as in Comparative Example 1 except that 40 parts by mass of emulsion polymerization SBR-1 and 60 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Comparative Example 3 Kneading was carried out in the same manner as in Comparative Example 1 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Comparative Example 4 Kneading was carried out in the same manner as in Comparative Example 1 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Comparative Example 5 Kneading was carried out in the same manner as in Comparative Example 1 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 1.
- Example 5 In the first stage of kneading, kneading was carried out in the same manner as in Example 1 except that 50 parts by mass of silica-2 was used as silica (B). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Example 8 Kneading was carried out in the same manner as in Example 5 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Comparative Example 6 In the first stage of kneading, 1 part by weight of 1,3-diphenylguanidine is not added, and in the final stage of kneading, neither 2 parts by weight of stearic acid or 1 part by weight of anti-aging agent 6PPD is added. Kneaded in the same manner as in Example 5 except that 100 parts by mass of solution-polymerized SBR-2 was used as the rubber component (A) in the stage, and 2 parts by mass of stearic acid and 1 part by mass of anti-aging agent 6PPD were added. . The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Comparative Example 7 Kneading was carried out in the same manner as in Comparative Example 6 except that 40 parts by mass of emulsion polymerization SBR-1 and 60 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Comparative Example 8 Kneading was carried out in the same manner as in Comparative Example 6 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Comparative Example 9 Kneading was carried out in the same manner as in Comparative Example 6 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Comparative Example 10 Kneading was carried out in the same manner as in Comparative Example 6 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 2.
- Example 9 In the first stage of kneading, kneading was carried out in the same manner as in Example 1 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- Example 10 Kneading was carried out in the same manner as in Example 1 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- Example 11 Kneading was carried out in the same manner as in Example 1 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- Example 12 Kneading was conducted in the same manner as in Example 1 except that 100 parts by mass of natural rubber was used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- Comparative Example 11 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 3.
- Example 13 In the first stage of kneading, 25 parts by mass of emulsion polymerization SBR-1 and 75 parts by mass of solution polymerization SBR-2, 30 parts by mass of carbon black N220, silica (B) as a rubber component (A) in a Banbury mixer.
- silica-1 and silane coupling agent (C) 2.4 parts by mass of silane coupling agent Si75 and 30 parts by mass of aromatic oil were kneaded for 60 seconds, and then a vulcanization accelerator (D ) And 1 part by weight of 1,3-diphenylguanidine, which is a guanidine, were further kneaded and adjusted so that the maximum temperature of the rubber composition in the first stage of kneading was 150 ° C.
- Example 14 Kneading was carried out in the same manner as in Example 13 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Example 15 Kneading was carried out in the same manner as in Example 13 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Example 16 Kneading was carried out in the same manner as in Example 13 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A) and that the maximum temperature of the rubber composition in the first stage of kneading was adjusted to 170 ° C.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Comparative Example 15 In the first stage of kneading, 1 part by weight of 1,3-diphenylguanidine is not added, and in the final stage of kneading, neither 2 parts by weight of stearic acid or 1 part by weight of anti-aging agent 6PPD is added. Kneaded in the same manner as in Example 13, except that 100 parts by mass of solution-polymerized SBR-2 was used as the rubber component (A) in the stage, and 2 parts by mass of stearic acid and 1 part by mass of anti-aging agent 6PPD were added. .
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Comparative Example 17 Kneading was carried out in the same manner as in Comparative Example 15 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Comparative Example 18 The rubber components (A) were kneaded in the same manner as in Comparative Example 15 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used. The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Comparative Example 19 Kneading was carried out in the same manner as in Comparative Example 15 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 4.
- Example 17 In the first stage of kneading, 25 parts by mass of emulsion polymerization SBR-1 and 75 parts by mass of solution polymerization SBR-2, 10 parts by mass of carbon black N220, silica (B) as a rubber component (A) in a Banbury mixer. As a vulcanization accelerator (D) after kneading 75 parts by weight of silica-1 and 6 parts by weight of silane coupling agent Si75 as a silane coupling agent (C) and 30 parts by weight of aromatic oil for 60 seconds.
- a vulcanization accelerator (D) after kneading 75 parts by weight of silica-1 and 6 parts by weight of silane coupling agent Si75 as a silane coupling agent (C) and 30 parts by weight of aromatic oil for 60 seconds.
- Example 18 Kneading was carried out in the same manner as in Example 17 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Example 19 Kneading was carried out in the same manner as in Example 17 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Example 20 Kneading was carried out in the same manner as in Example 17 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A) and that the maximum temperature of the rubber composition in the first stage of kneading was adjusted to 170 ° C.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Comparative Example 20 In the first stage of kneading, 1 part by weight of 1,3-diphenylguanidine is not added, and in the final stage of kneading, neither 2 parts by weight of stearic acid or 1 part by weight of anti-aging agent 6PPD is added. Kneaded in the same manner as in Example 17 except that 100 parts by mass of solution-polymerized SBR-2 was used as the rubber component (A) in the stage, and 2 parts by mass of stearic acid and 1 part by mass of anti-aging agent 6PPD were added. .
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Comparative Example 21 Kneading was carried out in the same manner as in Comparative Example 20, except that 40 parts by mass of emulsion polymerization SBR-1 and 60 parts by mass of solution polymerization SBR-2 were used as rubber components.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Comparative Example 22 Kneading was carried out in the same manner as in Comparative Example 20, except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Comparative Example 23 Kneading was carried out in the same manner as in Comparative Example 20, except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Comparative Example 24 Kneading was carried out in the same manner as in Comparative Example 20, except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 5.
- Example 21 In the first stage of kneading, 25 parts by mass of emulsion polymerization SBR-1 and 75 parts by mass of solution polymerization SBR-2, 5 parts by mass of carbon black N220, silica (B) as a rubber component (A) in a Banbury mixer. As a vulcanization accelerator (D) after kneading 100 parts by mass of silica-1 and 8 parts by mass of silane coupling agent Si75 as a silane coupling agent (C) and 40 parts by mass of aromatic oil for 60 seconds.
- a vulcanization accelerator (D) As a vulcanization accelerator (D) after kneading 100 parts by mass of silica-1 and 8 parts by mass of silane coupling agent Si75 as a silane coupling agent (C) and 40 parts by mass of aromatic oil for 60 seconds.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Example 23 Kneading was carried out in the same manner as in Example 21 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Example 24 Kneading was carried out in the same manner as in Example 21 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A) and the maximum temperature of the rubber composition in the first stage of kneading was adjusted to 170 ° C.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Comparative Example 25 In the first stage of kneading, 1 part by weight of 1,3-diphenylguanidine is not added, and in the final stage of kneading, neither 2 parts by weight of stearic acid or 1 part by weight of anti-aging agent 6PPD is added. Kneaded in the same manner as in Example 21, except that 100 parts by mass of solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of anti-aging agent 6PPD were added. . The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Comparative Example 26 Kneading was carried out in the same manner as in Comparative Example 25 except that 40 parts by mass of emulsion polymerization SBR-1 and 60 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Comparative Example 27 Kneading was carried out in the same manner as in Comparative Example 25 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Comparative Example 28 Kneading was carried out in the same manner as in Comparative Example 25 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Comparative Example 29 Kneading was carried out in the same manner as in Comparative Example 25 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 6.
- Example 25 In the first stage of kneading, 25 parts by mass of emulsion polymerization SBR-1 and 75 parts by mass of solution polymerization SBR-2, 5 parts by mass of carbon black N220, silica (B) as a rubber component (A) in a Banbury mixer.
- silica-1 and silane coupling agent (C) 9.6 parts by mass of silane coupling agent Si75 and 50 parts by mass of aromatic oil were kneaded for 60 seconds, and then a vulcanization accelerator (D ) And 1 part by weight of 1,3-diphenylguanidine, which is a guanidine, were further kneaded and adjusted so that the maximum temperature of the rubber composition in the first stage of kneading was 150 ° C.
- Example 26 Kneading was carried out in the same manner as in Example 25 except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Example 27 Kneading was carried out in the same manner as in Example 25 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Example 28 Kneading was carried out in the same manner as in Example 25 except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A) and that the maximum temperature of the rubber composition in the first stage of kneading was adjusted to 170 ° C.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Comparative Example 30 In the first stage of kneading, 1 part by weight of 1,3-diphenylguanidine is not added, and in the final stage of kneading, neither 2 parts by weight of stearic acid or 1 part by weight of anti-aging agent 6PPD is added. Kneaded in the same manner as in Example 25 except that 100 parts by mass of solution-polymerized SBR-2 was used as the rubber component (A) in the stage, and 2 parts by mass of stearic acid and 1 part by mass of anti-aging agent 6PPD were added. .
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Comparative Example 31 Kneading was carried out in the same manner as in Comparative Example 30 except that 40 parts by mass of emulsion polymerization SBR-1 and 60 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Comparative Example 32 Kneading was carried out in the same manner as in Comparative Example 30, except that 50 parts by mass of emulsion polymerization SBR-1 and 50 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Comparative Example 33 Kneading was carried out in the same manner as in Comparative Example 30 except that 67 parts by mass of emulsion polymerization SBR-1 and 33 parts by mass of solution polymerization SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Comparative Example 34 Kneading was carried out in the same manner as in Comparative Example 30, except that 100 parts by mass of emulsion polymerization SBR-1 was used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 7.
- Example 29 In the first stage of kneading, kneading was carried out in the same manner as in Example 13 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Example 30 Kneading was carried out in the same manner as in Example 13 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Example 31 Kneading was carried out in the same manner as in Example 13 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Example 32 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Comparative Example 35 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Comparative Example 36 Kneading was carried out in the same manner as in Comparative Example 15 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Comparative Example 37 Kneading was carried out in the same manner as in Comparative Example 15 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Comparative Example 38 Kneading was carried out in the same manner as in Comparative Example 15 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 8.
- Example 33 In the first stage of kneading, kneading was carried out in the same manner as in Example 17 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Example 34 Kneading was carried out in the same manner as in Example 17 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Example 35 Kneading was carried out in the same manner as in Example 17 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Example 36 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Comparative Example 39 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Comparative Example 40 Kneading was carried out in the same manner as in Comparative Example 20, except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Comparative Example 41 Kneading was carried out in the same manner as in Comparative Example 20, except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Comparative Example 42 Kneading was carried out in the same manner as in Comparative Example 20, except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 9.
- Example 37 In the first stage of kneading, kneading was carried out in the same manner as in Example 21 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Example 38 Kneading was carried out in the same manner as in Example 21 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Example 39 Kneading was carried out in the same manner as in Example 21 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Example 40 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Comparative Example 43 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Comparative Example 44 Kneading was carried out in the same manner as in Comparative Example 25 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Comparative Example 45 Kneading was carried out in the same manner as in Comparative Example 25 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Comparative Example 46 Kneading was carried out in the same manner as in Comparative Example 25 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 10.
- Example 41 In the first stage of kneading, kneading was carried out in the same manner as in Example 25 except that 25 parts by mass of natural rubber and 75 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- Example 42 Kneading was carried out in the same manner as in Example 25 except that 50 parts by mass of natural rubber and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- Example 43 Kneading was carried out in the same manner as in Example 25 except that 67 parts by mass of natural rubber and 33 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A).
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- Example 44 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- Comparative Example 47 It knead
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- the average flocculated aggregate area and low exothermic property (tan ⁇ index) of the obtained vulcanized rubber composition were evaluated by the above methods. The results are shown in Table 11.
- each of the rubber compositions of Examples 1 to 12 has a low exothermic property (tan ⁇ index) as compared with the rubber compositions to be compared in Comparative Examples 1 to 14. ) was good. Further, as is apparent from Tables 4 to 11, the rubber compositions of Examples 13 to 44 are all less heat-generating (tan ⁇ index) than the rubber compositions to be compared in Comparative Examples 15 to 50. ) was good.
- the rubber composition of the present invention is excellent in low heat build-up, various pneumatic tires for passenger cars, light trucks, light passenger cars, light trucks and large vehicles (for trucks, buses, construction vehicles, etc.) These members are particularly preferably used as a tread member of a pneumatic radial tire.
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Abstract
Description
このような発熱性の低いゴム組成物を得る方法として、充填材としてシリカ等の無機充填材を使用する方法が知られている。
しかし、シリカ配合ゴム組成物において、シリカはゴム組成物中で凝集してしまうため(シリカ表面の水酸基が原因で凝集してしまうため)、凝集を防止するためにシランカップリング剤が用いられる。
従って、シランカップリング剤を配合して上記問題を好適に解決するために、シランカップリング剤のカップリング機能の活性を高める目的で種々の試みがなされている。
また、特許文献2では、基本成分として、少なくとも(i)1種のジエンエラストマー、(ii)補強性充填剤として白色充填剤、(iii)カップリング剤(白色充填剤/ジエンエラストマー)としてポリ硫化アルコキシシランを、(iv)ジチオリン酸亜鉛及び(v)グアニジン誘導体と一緒に含むゴム組成物が開示されている。
特許文献3では、少なくとも、(i) ジエンエラストマー、(ii) 強化充填剤としての無機充填剤、(iii)(無機充填剤/ジエンエラストマー)カップリング剤としての多硫化アルコキシシラン(PSAS)をベースとし、(iv) アルジミン(R-CH=N-R)及び(v) グアニジン誘導体とが併用されているゴム組成物が記載されている。
特許文献7では、ゴム組成物に、臭化n-ヘキサデシルトリメチルアンモニウム(CTAB)吸着比表面積が好ましくは60~250×102m2/kgであるシリカとカテキンを含む茶抽出物とを配合することによりゴム組成物中にシリカの大きな凝集塊が存在しないようにする技術が提案されている。
さらに、特許文献8及び9には、ゴム成分中に含まれる充填材の分散状態が、暗視野法によって試料のカット面を観察する分散評価法において、全観察視野面積に対して、円相当径10μm以上の充填材凝集塊の占める面積の割合が、2.0%以下であること特徴とするゴム組成物が開示されている、
しかしながら、シリカを含有するゴム組成物において、低発熱性をさらに向上する技術が要望されている。
すなわち、本発明は、乳化重合により合成されたジエン系ゴム及び天然ゴムから選ばれる少なくとも1種のゴム10質量%以上及び他のジエン系ゴム90質量%以下からなるゴム成分(A)、ASTM D3765-92記載の方法に準拠して測定された臭化n-ヘキサデシルトリメチルアンモニウム(CTAB)吸着比表面積が140m2/g以上且つ180m2/g未満であるシリカ(B)、ポリスルフィド化合物及びチオエステル化合物から少なくとも1種選ばれるシランカップリング剤(C)及び加硫促進剤(D)を含むゴム組成物であって、加硫後の該ゴム組成物の該シリカの平均凝集アグリゲート面積(nm2)が2300以下であることを特徴とするゴム組成物である。
[平均凝集アグリゲート面積の測定法:
加硫後のゴム組成物試料の上面を、集束イオンビームを用いて、該試料の上面に対し角度38°をなす方向に切削した後、切削により形成された該試料の平滑面を、該平滑面に対し垂直な方向から走査型電子顕微鏡を用いて、加速電圧5kVで撮影する。得られた画像を、Otsu法により該試料のゴム部分と充填材であるシリカ部分との2値化像に変換して得られた2値化像に基づき、シリカ部分の凝集アグリゲート面積を求め、シリカ部分の全表面積と凝集アグリゲートの個数とから、単位面積(3μm×3μm)あたりのシリカ部分の平均凝集アグリゲート面積を数平均(相加平均)により算出する。算出に当たり、画像の端(辺)に接している粒子はカウントせず、20ピクセル以下の粒子は、ノイズと見做しカウントしない。]
本発明のゴム組成物は、乳化重合により合成されたジエン系ゴム及び天然ゴムから選ばれる少なくとも1種のゴム10質量%以上及び他のジエン系ゴム90質量%以下からなるゴム成分(A)、ASTM D3765-92記載の方法に準拠して測定された臭化n-ヘキサデシルトリメチルアンモニウム(CTAB)吸着比表面積が140m2/g以上且つ180m2/g未満であるシリカ(B)、ポリスルフィド化合物及びチオエステル化合物から少なくとも1種選ばれるシランカップリング剤(C)及び加硫促進剤(D)を含むゴム組成物であって、加硫後の該ゴム組成物の該シリカの平均凝集アグリゲート面積(nm2)が2300以下であることを特徴とする。ゴム組成物の低発熱性をさらに向上する観点から、該シリカの平均凝集アグリゲート面積(nm2)は、2200以下であることが好ましく、2150以下であることがさらに好ましい。該シリカの平均凝集アグリゲート面積(nm2)は300以上であることが好ましく、300~2300がより好ましく、300~2200がさらに好ましく、300~2150が特に好ましい。
FIB-SEMとしては、FEI社製、商品名「NOVA200」(登録商標)、SII Nano Technology Inc.製、商品名「SMI-3050MS2」(登録商標)などが挙げられ、FEI社製、商品名「NOVA200」(登録商標)が好ましい。
2値化像への変換は、Otsu法による画像処理装置を用いる。
次に、Otsu法を用いて、得られた画像の2値化の閾値を決定する。これによる該試料のゴム部分と充填材であるシリカ部分との2値化像に変換して得られた2値化像に基づき、シリカ部分の凝集アグリゲート面積を求め、シリカ部分の全表面積と凝集アグリゲートの個数とから、単位面積(3μm×3μm)あたりのシリカ部分の平均凝集アグリゲート面積を数平均(相加平均)により算出する。算出に当たり、画像の端(辺)に接している粒子はカウントせず、20ピクセル以下の粒子は、ノイズと見做しカウントしない。
図1は、本発明に係る平均凝集アグリゲート面積の測定法により、本発明のゴム組成物中のシリカの凝集アグリゲートを撮影したFIB-SEM画像の一例を示す写真であり、図2は、図1に示す画像の2値化像の一例を示す写真である。
また、図3は、図1と同じ方法によりシリカの凝集アグリゲートを撮影したFIB-SEM画像の他の参考例を示す写真であり、図4は、図3に示す画像の2値化像の一例を示す写真である。
本発明における凝集アグリゲートは、通常数十ミクロンから数百ミクロンの大きさと考えられているアグロメレート(二次凝集体)と比較してはるかに小さく、両者は全く異なる概念である。
本発明のゴム組成物に用いられるゴム成分(A)は、乳化重合により合成されたジエン系ゴム及び天然ゴムから選ばれる少なくとも1種のゴム10質量%以上及び他のジエン系ゴム90質量%以下からなるものであるが、乳化重合により合成されたジエン系ゴム及び天然ゴムから選ばれる少なくとも1種のゴム10質量%を超え、かつ他のジエン系ゴム90質量%未満であることが好ましい。
乳化剤としては、例えば、炭素数10以上の長鎖脂肪酸塩及び/又はロジン酸塩が用いられる。具体的には、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸などのカリウム塩またはナトリウム塩などが例示される。
ラジカル重合開始剤としては、例えば、過硫酸アンモニウム、過硫酸カリウムなどのような過硫酸塩;過硫酸アンモニウムと硫酸第二鉄との組合わせ、有機過酸化物と硫酸第二鉄との組み合わせ、及び過酸化水素と硫酸第二鉄との組み合わせなどのようなレドックス系開始剤;などが用いられる。
ジエン系ゴムの分子量を調節するために、連鎖移動剤を添加することもできる。連鎖移動剤としては、例えばt-ドデシルメルカプタン、n-ドデシルメルカプタンなどのメルカプタン類、α-メチルスチレンダイマー、四塩化炭素、チオグリコール酸、ジテルペン、ターピノーレン、γ-テルビネン類などを用いることができる。
乳化重合の温度は、用いられるラジカル重合開始剤の種類によって適宜選択することができるが、通常、0~100℃、好ましくは0~60℃である。重合様式は、連続重合、回分重合等のいずれでも構わない。
乳化重合において重合転化率が大きくなると、ゲル化する傾向がみられる。そのため、重合転化率を90%以下に抑えるのが好ましく、特に、転化率50~80%の範囲で重合を停止するのが好ましい。重合反応の停止は、通常、所定の転化率に達した時点で、重合系に重合停止剤を添加することによって行われる。重合停止剤としては、例えば、ジエチルヒドロキシルアミンやヒドロキシルアミンなどのようなアミン系化合物、ヒドロキノンやベンゾキノンなどのようなキノン系化合物、亜硝酸ナトリウム、ソジウムジチオカーバメートなどが用いられる。
重合反応停止後、得られた重合体ラテックスから必要に応じて未反応モノマーを除去し、次いで、必要に応じて硝酸、硫酸等のような酸を添加混合してラテックスのpHを所定の値に調整した後に、塩化ナトリウム、塩化カルシウム、塩化カリウムなどのような塩を凝固剤として添加混合し、重合体をクラムとして凝固させたのち回収する。クラムは洗浄、脱水後、バンドドライヤーなどで乾燥し、目的とするジエン系ゴムを得ることができる。
乳化重合SBRは、スチレン成分が5~50質量%の範囲で含まれることが好ましく、10~50質量%の範囲で含まれることがより好ましく、15~45質量%の範囲で含まれることがさらに好ましい。
これらの他のジエン系ゴムは、1種単独でも、2種以上のブレンドとして用いても良い。
このアニオン重合に使用する重合開始剤は、アルカリ金属化合物であるが、リチウム化合物が好ましい。リチウム化合物としては、通常のリチウム化合物(特に、ヒドロカルビルリチウムやリチウムアミド化合物)だけでなく、スズ変性溶液重合SBRを得る場合は、スズ原子を有するリチウム化合物(例えば、トリブチルスズリチウム,トリオクチルスズリチウムなどのトリオルガノスズリチウム化合物)を使用しても良い。
スズ変性溶液重合SBRは、上述のようにして得られた無変性溶液重合SBRの重合反応完了後、重合停止前にスチレン-ブタジエン共重合体の重合活性末端に、変性剤としてのスズ化合物を反応させることにより得られる。
上記スズ化合物としては、例えば四塩化スズ,トリブチルスズクロリド,トリオクチルスズクロリド,ジオクチルスズジクロリド,ジブチルスズジクロリド,塩化トリフェニルスズなどが挙げられる。
本発明のゴム組成物に用いられるシリカ(B)としては市販のあらゆるものが使用でき、なかでも湿式シリカ、乾式シリカ、コロイダルシリカを用いるのが好ましく、湿式シリカを用いるのがさらに好ましい。湿式シリカは、沈降法シリカとゲル法シリカに類別されるが、混練のせん断によりゴム組成物中に分散されやすく、分散後の表面反応による補強性に優れる沈降法シリカが特に好ましい。
また、シリカ(B)のCTAB吸着比表面積は、140m2/g以上且つ180m2/g未満であることを特徴とする。CTAB吸着比表面積がこの範囲内である沈降法シリカとしては、東ソー・シリカ(株)製、商品名「ニップシールAQ」(登録商標)(CTAB吸着比表面積=160m2/g)、Rhodia(株)製、商品名「Zeosil 1165」(登録商標)(CTAB吸着比表面積=160m2/g)等が好適に挙げられる。
また、本発明のゴム組成物において、ゴム成分(A)100質量部に対して、シリカ(B)及び所望により加えられるカーボンブラック等からなる充填材を25~170質量部含有することが好ましい。25質量部以上であれば、ゴム組成物の補強性向上の観点から好ましく、170質量部以下であれば、転がり抵抗低減の観点から好ましい。
前記充填材中、シリカ(B)が40質量%以上であることがウェット性能と転がり抵抗の両立の観点から好ましく、70質量%以上であることがさらに好ましい。
本発明のゴム組成物に用いられるシランカップリング剤(C)としては、ポリスルフィド化合物及びチオエステル化合物から少なくとも1種選ばれるシランカップリング剤であることを要する。ポリスルフィド化合物及びチオエステル化合物は、混練中のやけ(スコーチ)が起こらず、加工性を良好にできるため好ましい。
ポリスルフィド化合物及びチオエステル化合物から少なくとも1種選ばれるシランカップリング剤(C)として、下記一般式(I)~(IV)で表わされる化合物からなる群から1種以上選択される化合物であることが好ましい。
本発明方法に係るゴム組成物は、このようなシランカップリング剤(C)を用いることにより、ゴム加工時の作業性に更に優れると共に、より耐摩耗性の良好な空気入りタイヤを与えることができる。
ポリスルフィド化合物の好適例が、下記一般式(I)又は(III)で表わされる化合物であり、チオエステル化合物の好適例が、下記一般式(II)又は(IV)で表わされる化合物である。
以下、下記一般式(I)~(IV)を順に説明する。
上記一般式(II)におけるR12の例としては、メチレン基,エチレン基,トリメチレン基,テトラメチレン基,ペンタメチレン基,ヘキサメチレン基,オクタメチレン基,デカメチレン基,ドデカメチレン基等が挙げられる。
(-S-R17-S-)、(-R18-Sm1-R19-)及び(-R20-Sm2-R21-Sm3-R22-)のいずれかの二価の基(R17~R22は同一でも異なっていても良く、各々炭素数1~20の二価の炭化水素基、二価の芳香族基又は硫黄及び酸素以外のヘテロ元素を含む二価の有機基であり、m1、m2、m3は同一でも異なっていても良く、各々平均値として1以上4未満である。)であり、kは同一でも異なっていても良く、各々平均値として1~6であり、s及びtは同一でも異なっていても良く、各々平均値として0~3、但しs及びtの双方が3であることはない。
平均組成式(CH3CH2O)3Si-(CH2)3-S2-(CH2)6-S2-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S2-(CH2)10-S2-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S3-(CH2)6-S3-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S4-(CH2)6-S4-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S-(CH2)6-S2-(CH2)6-S-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S-(CH2)6-S2.5-(CH2)6-S-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S-(CH2)6-S3-(CH2)6-S-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S-(CH2)6-S4-(CH2)6-S-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S-(CH2)10-S2-(CH2)10-S-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S4-(CH2)6-S4-(CH2)6-S4-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S2-(CH2)6-S2-(CH2)6-S2-(CH2)3-Si(OCH2CH3)3、
平均組成式(CH3CH2O)3Si-(CH2)3-S-(CH2)6-S2-(CH2)6-S2-(CH2)6-S-(CH2)3-Si(OCH2CH3)3等で表される化合物が好適に挙げられる。
上記一般式(III)で表わされるシランカップリング剤(C)の合成例は、例えば、国際公開2004-000930号に記載されている。
また、化学式(VI)で表されるシランカップリング剤としては、[Momentive Performance Materials Inc. 製、商品名「NXT Ultra Low-V Silane」(登録商標)]を同様に市販品として入手することができる。
更に、化学式(VII)で表されるシランカップリング剤としては、[Momentive Performance Materials Inc. 製、商品名「NXT-Z」(登録商標)]を挙げることができる。
上記一般式(II)、化学式(V)及び化学式(VI)で得られるシランカップリング剤は、保護されたメルカプト基を有するので、加硫工程以前の工程での加工中に初期加硫(スコーチ)の発生を防止することができるため、加工性が良好となる。
また、化学式(V)、(VI)及び(VII)で得られるシランカップリング剤はアルコキシシラン炭素数が多いため、揮発性化合物VOC(特にアルコール)の発生が少なく、作業環境上好ましい。また、化学式(VII)のシランカップリング剤はタイヤ性能として低発熱性を得ることから更に好ましい。
本発明においては、シランカップリング剤(C)は一種を単独で用いても良く、二種以上を組み合わせて用いても良い。
本発明のゴム組成物のシランカップリング剤(C)の配合量は、シリカの1~20質量%であることが好ましい。1質量%未満ではゴム組成物の低発熱性向上の効果が発揮しにくくなり、20質量%を超えると、ゴム組成物のコストが過大となり、経済性が低下するからである。更にはシリカの3~20質量%であることがより好ましく、シリカの4~10質量%であることが特に好ましい。
(1)ゴム組成物を複数段階で混練し、混練の第一段階でゴム成分(A)、シリカ(B)の全部又は一部、シランカップリング剤(C)の全部又は一部及び加硫促進剤(D)を加えて混練し、且つ該第一段階におけるゴム組成物中の有機酸化合物のモル量を加硫促進剤(D)のモル量の1.5倍以下に制限するゴム組成物の製造方法。この場合、加硫促進剤(D)が、グアニジン類、スルフェンアミド類及びチアゾール類から選択される少なくとも一種であることが好ましい。
(2)ゴム組成物を複数段階で混練し、混練の第一段階で、ゴム成分(A)、シリカ(B)の全部又は一部、及びシランカップリング剤(C)の全部又は一部を混練りした後、該第一段階の途中で加硫促進剤(D)を加えて更に混練するゴム組成物の製造方法。この場合、加硫促進剤(D)が、グアニジン類、スルフェンアミド類、チアゾール類、チウラム類、ジチオカルバミン酸塩類、チオウレア類及びキサントゲン酸塩類から選ばれる少なくとも一種であることが好ましい。
(3)ゴム組成物を3段階以上の混練段階で混練し、混練の第一段階(X)でゴム成分(A)、シリカ(B)の全部又は一部、及びシランカップリング剤(C)の全部又は一部を混練し、混練の第二段階以降でかつ最終段階より前の段階(Y)で加硫促進剤(D)を加えて混練し、混練の最終段階(Z)で加硫剤を加えて混練するゴム組成物の製造方法。この場合、加硫促進剤(D)が、グアニジン類、スルフェンアミド類、チアゾール類、チウラム類、ジチオカルバミン酸塩類、チオウレア類及びキサントゲン酸塩類から選ばれる少なくとも一種であることが好ましい。
(4)ゴム組成物を複数段階で混練し、混練の第一段階で、ゴム成分(A)、シリカ(B)の全部又は一部、及びシランカップリング剤(C)の全部又は一部、及び加硫促進剤(D)を混練するゴム組成物の製造方法。この場合、加硫促進剤(D)が、グアニジン類、スルフェンアミド類、チアゾール類、チウラム類、ジチオカルバミン酸塩類、チオウレア類及びキサントゲン酸塩類から選ばれる少なくとも一種であることが好ましい。(4)において、更に下記の(5)とすることが望ましい。
(5)ゴム組成物を複数段階で混練し、混練の第一段階でゴム成分(A)、シリカ(B)の全部又は一部、シランカップリング剤(C)の全部又は一部及び該加硫促進剤(D)を加えて混練し、且つ該第一段階におけるゴム組成物中の有機酸化合物のモル量を加硫促進剤(D)のモル量の1.5倍以下に制限するゴム組成物の製造方法。この場合、加硫促進剤(D)が、グアニジン類、スルフェンアミド類、チアゾール類、チウラム類、ジチオカルバミン酸塩類、チオウレア類及びキサントゲン酸塩類から選択される少なくとも一種であることが好ましい。
第一段階、第二段階などの最終段階より前の混練段階におけるゴム組成物の最高温度は120~190℃であることが好ましく、130~175℃であることがより好ましく、150~170℃であることがさらに好ましい。なお、混練時間は0.5分から20分であることが好ましく、0.5分から10分であることがより好ましく、0.5分から5分であることがさらに好ましい。
また、混練の最終段階とは、架橋に関わる薬品(加硫剤、加硫促進剤)を配合し、混練する工程をいう。この最終段階におけるゴム組成物の最高温度は60~140℃であることが好ましく、80~120℃であることがより好ましく、100~120℃であることがさらに好ましい。なお、混練時間は0.5分から20分であることが好ましく、0.5分から10分であることがより好ましく、0.5分から5分であることがさらに好ましい。
本発明のゴム組成物に用いられる加硫促進剤(D)として、グアニジン類、スルフェンアミド類、チアゾール類、チウラム類、ジチオカルバミン酸塩類、チオウレア類及びキサントゲン酸塩類が好ましく挙げられる。
本発明のゴム組成物に用いられるグアニジン類としては、1,3-ジフェニルグアニジン、1,3-ジ-o-トリルグアニジン、1-o-トリルビグアニド、ジカテコールボレートのジ-o-トリルグアニジン塩、1,3-ジ-o-クメニルグアニジン、1,3-ジ-o-ビフェニルグアニジン、1,3-ジ-o-クメニル-2-プロピオニルグアニジン等が挙げられ、1,3-ジフェニルグアニジン、1,3-ジ-o-トリルグアニジン及び1-o-トリルビグアニドは反応性が高いので好ましい。
本発明のゴム組成物に配合される有機酸化合物としては、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、アラキジン酸、ベヘン酸、リグノセリン酸、カプリン酸、ペラルゴン酸、カプリル酸、エナント酸、カプロン酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、ネルボン酸等の飽和脂肪酸及び不飽和脂肪酸並びにロジン酸や変性ロジン酸等の樹脂酸などから選ばれる有機酸、前記有機酸の金属塩又はエステル、フェノール誘導体などが挙げられる。
本発明においては、加硫促進助剤としての機能を十分に発揮する必要があることから有機酸化合物中の50モル%以上がステアリン酸であることが好ましい。
本発明における混練装置として、バンバリーミキサー、ロール、インテンシブミキサー等が用いられる。
なお、加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を下記の方法により評価した。
加硫後のゴム組成物試料として、加硫ゴムシートをカミソリでカットすることにより作製した。その形状は5mm×5mm×厚み1mmであった。
FIB-SEM(FEI社製、NOVA200)を用いて、該試料の上面を、電圧30kVの条件で集束イオンビームを用いて、該試料の上面に対し角度38°をなす方向に切削した。切削により形成された該試料の平滑面を、該平滑面に対し垂直な方向からSEMを用いて、加速電圧5kVで撮影した。得られた画像を、Otsu法により該試料のゴム部分と充填材であるシリカ部分との2値化像に変換して得られた2値化像に基づき、シリカ部分の凝集アグリゲート面積を求め、シリカ部分の全表面積と凝集アグリゲートの個数とから、単位面積(3μm×3μm)あたりのシリカ部分の平均凝集アグリゲート面積を数平均(相加平均)により算出した。算出に当たり、画像の端(辺)に接している粒子はカウントせず、20ピクセル以下の粒子は、ノイズと見做しカウントしなかった。
粘弾性測定装置(レオメトリックス社製)を使用し、温度60℃、動歪み5%、周波数15Hzでtanδを測定した。比較例1、6、11、15、20、25、30、35、39、43又は47のtanδの逆数を100として下記式にて指数表示した。指数値が大きい程、低発熱性であり、ヒステリシスロスが小さいことを示す。
低発熱性指数={(比較例1、6、11、15、20、25、30、35、39、43又は47の加硫ゴム組成物のtanδ)/(供試加硫ゴム組成物のtanδ)}×100
(1)乳化重合SBR-1: JSR株式会社製、乳化重合スチレン-ブタジエン共重合体ゴム(SBR)、商品名「#1500」
(2)溶液重合SBR-2: 旭化成株式会社製、無変性溶液重合スチレン-ブタジエン共重合体ゴム(SBR)、商品名「タフデン2000」
(3)天然ゴム: RSS#3
(4)カーボンブラックN220: 旭カーボン株式会社製、商品名「#80」
(5)シリカ-1: Rhodia(株)製、商品名「Zeosil 1165」(登録商標)(CTAB吸着比表面積=160m2/g)
(6)シリカ-2: 東ソー・シリカ(株)製、商品名「ニップシールAQ」(登録商標)(CTAB吸着比表面積=160m2/g)
(7)シランカップリング剤Si75: ビス(3-トリエトキシシリルプロピル)ジスルフィド(平均硫黄鎖長:2.35)、Evonik社製シランカップリング剤、商品名「Si75」(登録商標)
(8)老化防止剤6PPD: N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン、大内新興化学工業株式会社製、商品名「ノクラック6C」
(9)1,3-ジフェニルグアニジン: 三新化学工業株式会社製、商品名「サンセラーD」
(10)老化防止剤TMDQ: 2,2,4-トリメチル-1,2-ジヒドロキノリン重合体、大内新興化学工業株式会社製、商品名「ノクラック224」
(11) 加硫促進剤MBTS: ジ-2-ベンゾチアゾリルジスルフィド、三新化学工業株式会社製、商品名「サンセラーDM」
(12) 加硫促進剤TBBS: N-tert-ブチル-2-ベンゾチアゾリルスルフェンアミド、三新化学工業株式会社製、商品名「サンセラーNS」
混練の第一段階において、バンバリーミキサーにて、ゴム成分(A)として25質量部の乳化重合SBR-1及び75質量部の溶液重合SBR-2、10質量部のカーボンブラックN220、シリカ(B)として50質量部のシリカ-1、シランカップリング剤(C)として4質量部のシランカップリング剤Si75及び30質量部のアロマティックオイル、を60秒混練した後に、加硫促進剤(D)としてグアニジン類である1質量部の1,3-ジフェニルグアニジンを加えて、さらに混練し、混練の第一段階におけるゴム組成物の最高温度が150℃になるように調整した。
次に、混練の最終段階において、2質量部のステアリン酸、1質量部の老化防止剤6PPD、1質量部の老化防止剤TMDQ、2.5質量部の亜鉛華、0.6質量部の1,3-ジフェニルグアニジン、1質量部の加硫促進剤MBTS、0.6質量部の加硫促進剤TBBS及び1.5質量部の硫黄を加えて混練の最終段階におけるゴム組成物の最高温度が110℃になるように調整した。
このゴム組成物から得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用い、混練の第一段階におけるゴム組成物の最高温度が170℃になるように調整した以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
混練の第一段階において1質量部の1,3-ジフェニルグアニジンを加えず、混練の最終段階において2質量部のステアリン酸及び1質量部の老化防止剤6PPDのいずれも加えず、混練の第一段階においてゴム成分(A)として100質量部の溶液重合SBR-2を用い、かつ2質量部のステアリン酸及び1質量部の老化防止剤6PPDを加えた以外は、実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として40質量部の乳化重合SBR-1及び60質量部の溶液重合SBR-2を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第1表に示す。
混練の第一段階において、シリカ(B)として50質量部のシリカ-2を用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は実施例5と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は実施例5と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は実施例5と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
混練の第一段階において1質量部の1,3-ジフェニルグアニジンを加えず、混練の最終段階において2質量部のステアリン酸及び1質量部の老化防止剤6PPDのいずれも加えず、混練の第一段階においてゴム成分(A)として100質量部の溶液重合SBR-2を用い、かつ2質量部のステアリン酸及び1質量部の老化防止剤6PPDを加えた以外は、実施例5と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として40質量部の乳化重合SBR-1及び60質量部の溶液重合SBR-2を用いた以外は比較例6と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は比較例6と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は比較例6と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は比較例6と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第2表に示す。
混練の第一段階において、ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は実施例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は比較例1と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第3表に示す。
混練の第一段階において、バンバリーミキサーにて、ゴム成分(A)として25質量部の乳化重合SBR-1及び75質量部の溶液重合SBR-2、30質量部のカーボンブラックN220、シリカ(B)として30質量部のシリカ-1、シランカップリング剤(C)として2.4質量部のシランカップリング剤Si75及び30質量部のアロマティックオイル、を60秒混練した後に、加硫促進剤(D)としてグアニジン類である1質量部の1,3-ジフェニルグアニジンを加えて、さらに混練し、混練の第一段階におけるゴム組成物の最高温度が150℃になるように調整した。
次に、混練の最終段階において、2質量部のステアリン酸、1質量部の老化防止剤6PPD、1質量部の老化防止剤TMDQ、2.5質量部の亜鉛華、1質量部の加硫促進剤MBTS、0.6質量部の加硫促進剤TBBS及び1.5質量部の硫黄を加えて混練の最終段階におけるゴム組成物の最高温度が110℃になるように調整した。
このゴム組成物から得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用い、混練の第一段階におけるゴム組成物の最高温度が170℃になるように調整した以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
混練の第一段階において1質量部の1,3-ジフェニルグアニジンを加えず、混練の最終段階において2質量部のステアリン酸及び1質量部の老化防止剤6PPDのいずれも加えず、混練の第一段階においてゴム成分(A)として100質量部の溶液重合SBR-2を用い、かつ2質量部のステアリン酸及び1質量部の老化防止剤6PPDを加えた以外は、実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として40質量部の乳化重合SBR-1及び60質量部の溶液重合SBR-2を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第4表に示す。
混練の第一段階において、バンバリーミキサーにて、ゴム成分(A)として25質量部の乳化重合SBR-1及び75質量部の溶液重合SBR-2、10質量部のカーボンブラックN220、シリカ(B)として75質量部のシリカ-1、シランカップリング剤(C)として6質量部のシランカップリング剤Si75及び30質量部のアロマティックオイル、を60秒混練した後に、加硫促進剤(D)としてグアニジン類である1質量部の1,3-ジフェニルグアニジンを加えて、さらに混練し、混練の第一段階におけるゴム組成物の最高温度が150℃になるように調整した。
次に、混練の最終段階において、2質量部のステアリン酸、1質量部の老化防止剤6PPD、1質量部の老化防止剤TMDQ、2.5質量部の亜鉛華、0.6質量部の1,3-ジフェニルグアニジン、1質量部の加硫促進剤MBTS、0.6質量部の加硫促進剤TBBS及び1.5質量部の硫黄を加えて混練の最終段階におけるゴム組成物の最高温度が110℃になるように調整した。
このゴム組成物から得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用い、混練の第一段階におけるゴム組成物の最高温度が170℃になるように調整した以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
混練の第一段階において1質量部の1,3-ジフェニルグアニジンを加えず、混練の最終段階において2質量部のステアリン酸及び1質量部の老化防止剤6PPDのいずれも加えず、混練の第一段階においてゴム成分(A)として100質量部の溶液重合SBR-2を用い、かつ2質量部のステアリン酸及び1質量部の老化防止剤6PPDを加えた以外は、実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分として40質量部の乳化重合SBR-1及び60質量部の溶液重合SBR-2を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第5表に示す。
混練の第一段階において、バンバリーミキサーにて、ゴム成分(A)として25質量部の乳化重合SBR-1及び75質量部の溶液重合SBR-2、5質量部のカーボンブラックN220、シリカ(B)として100質量部のシリカ-1、シランカップリング剤(C)として8質量部のシランカップリング剤Si75及び40質量部のアロマティックオイル、を60秒混練した後に、加硫促進剤(D)としてグアニジン類である1質量部の1,3-ジフェニルグアニジンを加えて、さらに混練し、混練の第一段階におけるゴム組成物の最高温度が150℃になるように調整した。
次に、混練の最終段階において、2質量部のステアリン酸、1質量部の老化防止剤6PPD、1質量部の老化防止剤TMDQ、2.5質量部の亜鉛華、0.9質量部の1,3-ジフェニルグアニジン、1質量部の加硫促進剤MBTS、0.6質量部の加硫促進剤TBBS及び1.5質量部の硫黄を加えて混練の最終段階におけるゴム組成物の最高温度が110℃になるように調整した。
このゴム組成物から得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用い、混練の第一段階におけるゴム組成物の最高温度が170℃になるように調整した以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
混練の第一段階において1質量部の1,3-ジフェニルグアニジンを加えず、混練の最終段階において2質量部のステアリン酸及び1質量部の老化防止剤6PPDのいずれも加えず、混練の第一段階においてゴム成分(A)として100質量部の溶液重合SBR-2を用い、かつ2質量部のステアリン酸及び1質量部の老化防止剤6PPDを加えた以外は、実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として40質量部の乳化重合SBR-1及び60質量部の溶液重合SBR-2を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第6表に示す。
混練の第一段階において、バンバリーミキサーにて、ゴム成分(A)として25質量部の乳化重合SBR-1及び75質量部の溶液重合SBR-2、5質量部のカーボンブラックN220、シリカ(B)として125質量部のシリカ-1、シランカップリング剤(C)として9.6質量部のシランカップリング剤Si75及び50質量部のアロマティックオイル、を60秒混練した後に、加硫促進剤(D)としてグアニジン類である1質量部の1,3-ジフェニルグアニジンを加えて、さらに混練し、混練の第一段階におけるゴム組成物の最高温度が150℃になるように調整した。
次に、混練の最終段階において、2質量部のステアリン酸、1質量部の老化防止剤6PPD、1質量部の老化防止剤TMDQ、2.5質量部の亜鉛華、1.2質量部の1,3-ジフェニルグアニジン、1.2質量部の加硫促進剤MBTS、0.7質量部の加硫促進剤TBBS及び1.7質量部の硫黄を加えて混練の最終段階におけるゴム組成物の最高温度が110℃になるように調整した。
このゴム組成物から得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用い、混練の第一段階におけるゴム組成物の最高温度が170℃になるように調整した以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
混練の第一段階において1質量部の1,3-ジフェニルグアニジンを加えず、混練の最終段階において2質量部のステアリン酸及び1質量部の老化防止剤6PPDのいずれも加えず、混練の第一段階においてゴム成分(A)として100質量部の溶液重合SBR-2を用い、かつ2質量部のステアリン酸及び1質量部の老化防止剤6PPDを加えた以外は、実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として40質量部の乳化重合SBR-1及び60質量部の溶液重合SBR-2を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として50質量部の乳化重合SBR-1及び50質量部の溶液重合SBR-2を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として67質量部の乳化重合SBR-1及び33質量部の溶液重合SBR-2を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
ゴム成分(A)として100質量部の乳化重合SBR-1を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第7表に示す。
混練の第一段階において、ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は実施例13と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は比較例15と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第8表に示す。
混練の第一段階において、ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は実施例17と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は比較例20と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第9表に示す。
混練の第一段階において、ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は実施例21と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は比較例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第10表に示す。
混練の第一段階において、ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は実施例25と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として100質量部の天然ゴムを用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として25質量部の天然ゴム及び75質量部の溶液重合SBR-2を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として50質量部の天然ゴム及び50質量部の溶液重合SBR-2を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
ゴム成分(A)として67質量部の天然ゴム及び33質量部の溶液重合SBR-2を用いた以外は比較例30と同様に混練した。得られた加硫ゴム組成物の平均凝集アグリゲート面積及び低発熱性(tanδ指数)を上記の方法により評価した。結果を第11表に示す。
また、第4~11表より明らかなように、実施例13~44のゴム組成物は、比較例15~50中の対比すべきゴム組成物と比較して、いずれも低発熱性(tanδ指数)が良好であった。
Claims (7)
- 乳化重合により合成されたジエン系ゴム及び天然ゴムから選ばれる少なくとも1種のゴム10質量%以上及び他のジエン系ゴム90質量%以下からなるゴム成分(A)、ASTM D3765-92記載の方法に準拠して測定された臭化n-ヘキサデシルトリメチルアンモニウム(CTAB)吸着比表面積が140m2/g以上且つ180m2/g未満であるシリカ(B)、ポリスルフィド化合物及びチオエステル化合物から少なくとも1種選ばれるシランカップリング剤(C)及び加硫促進剤(D)を含むゴム組成物であって、加硫後の該ゴム組成物の該シリカの平均凝集アグリゲート面積(nm2)が2300以下であることを特徴とするゴム組成物。
[平均凝集アグリゲート面積の測定法:
加硫後のゴム組成物試料の上面を、集束イオンビームを用いて、該試料の上面に対し角度38°をなす方向に切削した後、切削により形成された該試料の平滑面を、該平滑面に対し垂直な方向から走査型電子顕微鏡を用いて、加速電圧5kVで撮影する。得られた画像を、Otsu法により該試料のゴム部分と充填材であるシリカ部分との2値化像に変換して得られた2値化像に基づき、シリカ部分の凝集アグリゲート面積を求め、シリカ部分の全表面積と凝集アグリゲートの個数とから、単位面積(3μm×3μm)あたりのシリカ部分の平均凝集アグリゲート面積を数平均(相加平均)により算出する。算出に当たり、画像の端(辺)に接している粒子はカウントせず、20ピクセル以下の粒子は、ノイズと見做しカウントしない。] - 前記他のジエン系ゴムが、溶液重合スチレン-ブタジエン共重合体ゴム、ポリブタジエンゴム及び合成ポリイソプレンゴムから選ばれる少なくとも1種のゴムである請求項1に記載のゴム組成物。
- 前記シランカップリング剤(C)が、下記一般式(I)~(IV)で表わされる化合物からなる群から1種以上選択される化合物である請求項1又は2に記載のゴム組成物。
(-S-R17-S-)、(-R18-Sm1-R19-)及び(-R20-Sm2-R21-Sm3-R22-)のいずれかの二価の基(R17~R22は同一でも異なっていても良く、各々炭素数1~20の二価の炭化水素基、二価の芳香族基又は硫黄及び酸素以外のヘテロ元素を含む二価の有機基であり、m1、m2、m3は同一でも異なっていても良く、各々平均値として1以上4未満である。)であり、kは同一でも異なっていても良く、各々平均値として1~6であり、s及びtは同一でも異なっていても良く、各々平均値として0~3、但しs及びtの双方が3であることはない。}
- 前記シランカップリング剤(C)が、上記一般式(I)で表わされる化合物である請求項3に記載のゴム組成物。
- 前記ゴム成分(A)100質量部に対して、前記シリカ(B)を25~150質量部含有する請求項1~4のいずれかに記載のゴム組成物。
- 前記シリカ(B)が、沈降法シリカである請求項1~5のいずれかに記載のゴム組成物。
- さらに、カーボンブラックを含有する請求項1~6のいずれかに記載のゴム組成物。
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CN201280031684.0A CN103635521B (zh) | 2011-04-28 | 2012-04-27 | 橡胶组合物 |
JP2013512505A JP5894587B2 (ja) | 2011-04-28 | 2012-04-27 | ゴム組成物の製造方法 |
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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 |
JP2016030789A (ja) * | 2014-07-29 | 2016-03-07 | 横浜ゴム株式会社 | 空気入りタイヤ |
JP2016030815A (ja) * | 2014-07-30 | 2016-03-07 | 横浜ゴム株式会社 | タイヤ用ゴム組成物 |
CN105473344A (zh) * | 2013-07-29 | 2016-04-06 | 株式会社普利司通 | 轮胎橡胶配混料的制造方法 |
WO2019012946A1 (ja) * | 2017-07-14 | 2019-01-17 | 株式会社ブリヂストン | ゴム組成物及びタイヤ |
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US20170029605A1 (en) * | 2015-07-27 | 2017-02-02 | Toyo Tire & Rubber Co., Ltd. | Rubber composition for tire and pneumatic tire |
CN113603941A (zh) * | 2021-08-02 | 2021-11-05 | 中策橡胶(建德)有限公司 | 一种含有白炭黑的橡胶复合材料及降低白炭黑在橡胶基体中团聚的混炼方法 |
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US20140142236A1 (en) | 2014-05-22 |
US8980990B2 (en) | 2015-03-17 |
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