WO2018105707A1 - Procédé de production d'une composition de caoutchouc pour pneu - Google Patents

Procédé de production d'une composition de caoutchouc pour pneu Download PDF

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Publication number
WO2018105707A1
WO2018105707A1 PCT/JP2017/044086 JP2017044086W WO2018105707A1 WO 2018105707 A1 WO2018105707 A1 WO 2018105707A1 JP 2017044086 W JP2017044086 W JP 2017044086W WO 2018105707 A1 WO2018105707 A1 WO 2018105707A1
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Prior art keywords
group
silica
mass
silane coupling
coupling agent
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PCT/JP2017/044086
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English (en)
Japanese (ja)
Inventor
慶介 村瀬
加奈子 植木
裕記 杉浦
亮佑 高木
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横浜ゴム株式会社
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Priority to JP2018555066A priority Critical patent/JP6702433B2/ja
Priority to CN201780075263.0A priority patent/CN110036061B/zh
Publication of WO2018105707A1 publication Critical patent/WO2018105707A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a method for producing a rubber composition for tires excellent in wet grip performance, low rolling resistance and wear resistance.
  • Silane coupling to improve the dispersibility of silica in diene rubbers in order to improve the abrasion resistance of rubber compositions containing silica and to improve wet grip performance and low rolling resistance. It is known to use a silica compounded with an agent or surface-treated in advance. Patent Documents 1 and 2 propose to improve the dispersibility of silica by sequentially charging and / or dividing and kneading the constituent components of the rubber composition. However, the use of surface-treated silica or the sequential introduction and / or split kneading have the problems that the number of processes increases and the production cost increases.
  • An object of the present invention is to provide a method for producing a rubber composition for a tire excellent in wet grip performance, low rolling resistance and wear resistance.
  • a tire rubber composition of the present invention In the method for producing a tire rubber composition of the present invention that achieves the above object, 80 to 180 parts by mass of silica is blended with 100 parts by mass of a diene rubber, and 5 to 18% by mass of a silane coupling agent is blended with respect to the amount of silica.
  • a method for producing a rubber composition characterized in that the silica and the silane coupling agent are charged together in a mixer and mixed, and then the diene rubber is charged and kneaded.
  • the silica and the silane coupling agent are charged into the mixer and mixed, and then the diene rubber is charged and kneaded, the silica and the silane coupling agent are easily brought into contact with each other.
  • high shear force can be applied to improve the dispersibility of silica, wet grip performance, low rolling resistance and wear resistance.
  • An excellent rubber composition for tires can be obtained.
  • carbon black and / or aroma oil can be added and mixed together with silica and a silane coupling agent.
  • the CTAB specific surface area of silica is preferably 150 to 300 m 2 / g. Further, 30% by mass or more of the modified diene rubber can be contained in 100% by mass of the diene rubber.
  • a method for producing a tire rubber composition includes a kneading step of mixing and kneading compounding agents excluding diene rubber, silica, silane coupling agent, carbon black, aroma oil, and vulcanizing compounding agent (No. 1). It comprises at least two steps: a one-step mixing step) and a step of cooling the mixture obtained in this kneading step and then mixing the vulcanizing compound (the final-stage mixing step).
  • the method for producing a rubber composition for a tire according to the present invention comprises the steps of mixing the above-described kneading step (first mixing step) by first putting the entire amount of silica and silane coupling agent into a mixer and mixing them. After the second charging / mixing step, the diene rubber is charged and kneaded into a mixer containing silica and a silane coupling agent, and is composed of at least two steps consisting of a second charging / mixing step.
  • the manufacturing method of the present invention starts the mixing process of the first stage by performing a step in which the total amount of silica and silane coupling agent is first introduced into a mixer and mixed.
  • the silica and the silane coupling agent are easily brought into contact with each other, and the silane coupling agent acts on the silica more effectively.
  • a man-hour can be reduced and production cost can be reduced.
  • the temperature of the mixer is lowered, then the temperature when kneading the diene rubber is lowered, the kneading strength in the mixer is increased, and the dispersibility of silica is increased. Can do better.
  • the temperature in the mixer increases due to the kneading of the diene rubber. Since the viscosity is lowered, a high shearing force cannot be applied when silica is added and kneaded later, so that the silica cannot be dispersed well.
  • the amount of silica and silane coupling agent to be added to the mixer is such that the silane coupling agent is 5 to 18% by mass, preferably 6 to 15% by mass with respect to the amount of silica.
  • Silica dispersion can be improved by setting the amount of the silane coupling agent to 5% by mass or more of the amount of silica. Further, by setting the blending amount of the silane coupling agent to 18% by mass or less of the silica amount, condensation between the silane coupling agents can be suppressed, and a rubber composition having desired hardness and strength can be obtained.
  • Mixing of the silica and the silane coupling agent can be performed using a mixer that is usually used for manufacturing a rubber composition for tires.
  • the type of rotor constituting the mixer may be either a meshing type or a non-meshing type.
  • the rotation speed of the rotor can be set to a normal rotation speed when the tire rubber composition is manufactured.
  • the temperature at which silica and the silane coupling agent are mixed is preferably 20 to 90 ° C., more preferably 30 to 70 ° C.
  • the step of adding and kneading the diene rubber can increase the shearing force and improve the dispersibility of the silica. .
  • the time for mixing the silica and the silane coupling agent can be preferably 5 seconds to 2 minutes, more preferably 20 seconds to 90 seconds. By setting the mixing time to 20 seconds or longer, the silica and the silane coupling agent can be mixed and brought into sufficient contact. Moreover, the productivity fall can be suppressed by making mixing time into 90 second or less.
  • carbon black and / or aroma oil can be added and mixed together with silica and a silane coupling agent, so that the rolling resistance can be further reduced and the wear resistance can be further increased.
  • Carbon black and aroma oil are preferably added to the mixer simultaneously with the silica and silane coupling agent.
  • the mixing conditions when carbon black and aroma oil are added can be the same as described above.
  • diene rubber is put into a mixer after mixing of silica and silane coupling agent and kneaded.
  • the diene rubber can be charged into the mixer within the range of normal charging conditions. Further, the conditions for kneading the silica and silane coupling agent and the diene rubber can be performed within a normal range.
  • the compounding agents excluding the vulcanizing compounding agent to be blended in the rubber composition for tires may be charged and mixed simultaneously with the diene rubber, or may be charged and mixed after the kneading of the diene rubber is finished.
  • Various additives commonly used in tire rubber compositions such as anti-aging agents, plasticizers, processing aids, liquid polymers, terpene resins, thermosetting resins, etc. Agents can be exemplified.
  • These compounding agents can be used in conventional general compounding amounts unless they are contrary to the object of the present invention.
  • fillers other than silica such as carbon black, are charged and kneaded at the same time as the introduction of the diene rubber.
  • the aroma oil may be added and mixed.
  • the kneading step for mixing and kneading the compounding agent excluding the diene rubber, silica, silane coupling agent, carbon black, aroma oil, and vulcanizing compounding agent
  • the obtained mixture is cooled and a step of mixing the vulcanizing compounding agent (final stage mixing step) is performed.
  • the vulcanizing compounding agent include vulcanization or crosslinking agents, vulcanization accelerators, vulcanization retarders and the like.
  • the method of mixing the vulcanizing compounding agent can be carried out in the same manner as the method for producing a normal tire rubber composition.
  • a second-stage mixing process or a third-stage mixing process in which the mixture obtained in the first-stage mixing process is further kneaded may be performed before the final-stage mixing process.
  • the second stage mixing process the kneaded product is taken out from the mixer of the first stage mixing process, cooled as necessary, and charged into the same mixer or another mixer for mixing.
  • the third stage mixing step the mixture obtained in the second stage mixing step is mixed in the same manner as described above.
  • the mixture obtained in each previous-stage mixing process may be added and mixed as it is, or a compounding agent may be additionally added to the mixture. May be mixed.
  • the tire rubber composition produced in the present invention is obtained by blending 80 to 180 parts by mass of silica with 100 parts by mass of diene rubber, and blending 5 to 18% by mass of the silane coupling agent with respect to the amount of silica.
  • the diene rubber is not particularly limited as long as it is usually used in a rubber composition for tires.
  • natural rubber isoprene rubber, butadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, styrene-isoprene- Examples thereof include butadiene rubber and acrylonitrile-butadiene rubber.
  • natural rubber, butadiene rubber, and styrene-butadiene rubber are preferable.
  • diene rubbers may be diene rubbers modified with a functional group having a hetero atom at the end and / or side chain of the molecular chain.
  • Hetero atoms include oxygen, nitrogen, silicon, and sulfur islands.
  • functional groups can be modified by epoxy groups, carboxy groups, amino groups, hydroxy groups, alkoxy groups, silyl groups, amide groups, oxysilyl groups, silanol groups, isocyanate groups, isothiocyanate groups, carbonyl groups, aldehyde groups, etc. Modified diene rubber may be used.
  • modified diene rubber examples include epoxy group-modified natural rubber, epoxy group-modified isoprene rubber, amino group-modified styrene-butadiene rubber, hydroxy group-modified styrene-butadiene rubber, silyl group-modified styrene-butadiene rubber, and oxysilyl group-modified styrene.
  • Examples include butadiene rubber, silanol group-modified styrene-butadiene rubber, imino group-modified styrene-butadiene rubber, carboxyl group-modified styrene-butadiene rubber, tin group-modified styrene-butadiene rubber, and epoxy group-modified styrene-butadiene rubber.
  • the modified diene rubber is preferably contained in 100% by mass of the diene rubber, preferably 30% by mass or more, more preferably 35% by mass or more. Further, the modified diene rubber may contain 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less. By making the content of the modified diene rubber 30% by mass or more, the dispersibility of silica can be further improved, and the wet grip performance, low rolling resistance and wear resistance can be further improved. .
  • silica examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. These may be used alone or in combination of two or more. Moreover, you may use the surface treatment silica in which the surface of the silica was surface-treated with a silane coupling agent.
  • the CTAB adsorption specific surface area of silica is not particularly limited, but is preferably 150 to 300 m 2 / g, more preferably 160 to 260 m 2 / g.
  • the CTAB adsorption specific surface area of silica is not particularly limited, but is preferably 150 to 300 m 2 / g, more preferably 160 to 260 m 2 / g.
  • Silica is blended in an amount of 80 to 180 parts by weight, preferably 90 to 160 parts by weight, based on 100 parts by weight of the diene rubber.
  • blending amount of silica 80 parts by mass or more, wet grip performance and low rolling resistance can be improved.
  • abrasion resistance is securable by making the compounding quantity of a silica into 180 mass parts or less.
  • the silane coupling agent is not particularly limited as long as it can be used for a rubber composition containing silica, and examples thereof include a sulfur-containing silane coupling agent and an amino group-containing silane coupling agent. .
  • the polysilane represented by the silane coupling agent represented by Formula (1) mentioned later and the average compositional formula of Formula (2) can be used preferably.
  • Examples of silane coupling agents include bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, and ⁇ -mercaptopropyltriethoxy.
  • Silane sulfur-containing silane coupling agents such as 3-octanoylthiopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxy Shi Emissions, N- can be exemplified (vinylbenzyl) -2-aminoethyl-3-hydrochloride salt of aminopropyltrimethoxysilane, the amino group-containing silane coupling agent and the like.
  • silane coupling agents such as 3-octanoylthio
  • a silane coupling agent represented by the following formula (1) can be preferably used.
  • p represents an integer of 1 to 3
  • q represents an integer of 1 to 3
  • r represents an integer of 1 to 15, and
  • t represents an integer of 0 to 2.
  • p is 2 to 3 in that the affinity for silica is high, the processability of the tire rubber composition is good, and the dispersibility of silica in the tire rubber composition is good. It is preferable that 2 is more preferable.
  • q is preferably 2 to 3 and more preferably 3 for the same reason.
  • r is preferably from 5 to 10, more preferably from 6 to 9, and even more preferably 7 from the viewpoint that the scorch time at the time of kneading the rubber composition for tire is good.
  • t represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • Such a silane coupling agent can be manufactured by a well-known method, for example, the method described in the international publication 99/09036 is mentioned. Examples of commercially available products include NXT silane manufactured by Momentive.
  • the sulfur-containing silane coupling agent is preferably a silane coupling agent having a mercapto group, and more preferably a polysiloxane represented by an average composition formula of the following formula (2).
  • A a (B) b (C) c (D) d (R 1 ) e SiO (4-2a-bcde) / 2 (2)
  • B contains a divalent organic group represented by the following formula (3)
  • B contains a monovalent hydrocarbon group having 5 to 20 carbon atoms
  • C contains a hydrolyzable group
  • D contains a mercapto group.
  • R 1 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, a to e are 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 3, 0 ⁇ d ⁇ 1, It is a real number that satisfies the relational expression of 0 ⁇ e ⁇ 2, 0 ⁇ 2a + b + c + d + e ⁇ 4.
  • *-(CH 2 ) n -Sx- (CH 2 ) n- * (3) In the above formula (3), n represents an integer of 1 to 10, x represents an integer of 1 to 6, and * represents a bonding position.
  • the polysiloxane (mercaptosilane compound) having an average composition formula represented by the general formula (2) has a siloxane skeleton as its skeleton.
  • the siloxane skeleton can be linear, branched, three-dimensional, or a combination thereof.
  • this polysiloxane necessarily contains at least one selected from a divalent organic group A containing a sulfide group and a monovalent hydrocarbon group B having 5 to 10 carbon atoms.
  • the silane coupling agent comprising polysiloxane having the average composition formula represented by the general formula (2) has a monovalent hydrocarbon group B having 5 to 10 carbon atoms
  • the mercapto group is protected and the Mooney scorch time
  • the processability is improved by having excellent compatibility with rubber.
  • the subscript b of the hydrocarbon group B in the general formula (2) is preferably 0.10 ⁇ b ⁇ 0.89.
  • Specific examples of the hydrocarbon group B preferably include monovalent hydrocarbon groups having 6 to 10 carbon atoms, more preferably 8 to 10 carbon atoms, such as hexyl group, octyl group, and decyl group.
  • the silane coupling agent made of polysiloxane having the average composition formula represented by the general formula (2) has a divalent organic group A containing a sulfide group, low exothermic property, workability (particularly Mooney scorch) Maintaining and prolonging time)
  • the subscript a of the divalent organic group A containing a sulfide group in the general formula (5) is preferably 0 ⁇ a ⁇ 0.50.
  • the divalent organic group A containing a sulfide group represents an integer of 1 to 10, and preferably an integer of 2 to 4.
  • X represents an integer of 1 to 6, and preferably an integer of 2 to 4.
  • the organic group A can be a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the silane coupling agent comprising polysiloxane having the average composition formula represented by the general formula (2) has excellent affinity and / or reactivity with silica by having a hydrolyzable group C.
  • the subscript c of the hydrolyzable group C in the general formula (2) is 1.2 ⁇ c ⁇ 2.0 because of low heat build-up, better processability, and better silica dispersibility. Good.
  • Specific examples of the hydrolyzable group C include an alkoxy group, a phenoxy group, a carboxyl group, an alkenyloxy group, and the like.
  • the hydrolyzable group C is preferably a group represented by the following general formula (4) from the viewpoint of improving the dispersibility of silica and further improving processability.
  • R 2 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms (arylalkyl group), or an alkenyl group having 2 to 10 carbon atoms, An alkyl group having 1 to 5 carbon atoms is preferable.
  • alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, octadecyl group and the like.
  • aryl group having 6 to 10 carbon atoms include a phenyl group and a tolyl group.
  • aralkyl group having 6 to 10 carbon atoms include a benzyl group and a phenylethyl group.
  • alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, a pentenyl group, and the like.
  • the silane coupling agent composed of polysiloxane having the average composition formula represented by the general formula (2) has an organic group D containing a mercapto group, thereby interacting with and / or reacting with a diene rubber. And low heat generation is excellent.
  • the subscript d of the organic group D containing a mercapto group is preferably 0.1 ⁇ d ⁇ 0.8.
  • the organic group D containing a mercapto group is preferably a group represented by the following general formula (5) from the viewpoint of improving the dispersibility of silica and further improving the workability.
  • *-(CH 2 ) m -SH (5) In the above general formula (5), m represents an integer of 1 to 10, and preferably an integer of 1 to 5. In the formula, * indicates a bonding position.
  • Specific examples of the group represented by the general formula (5) include * —CH 2 SH, * —C 2 H 4 SH, * —C 3 H 6 SH, * —C 4 H 8 SH, * —C. 5 H 10 SH, * - C 6 H 12 SH, * - C 7 H 14 SH, * - C 8 H 16 SH, * - C 9 H 18 SH, * - C 10 H 20 SH and the like.
  • R 1 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • examples of the hydrocarbon group R 1 include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the blending amount of the silane coupling agent is 5 to 18% by mass, preferably 6 to 15% by mass with respect to the mass of silica.
  • Silica dispersion can be improved by setting the amount of the silane coupling agent to 5% by mass or more of the amount of silica. Further, by setting the blending amount of the silane coupling agent to 18% by mass or less of the silica amount, condensation between the silane coupling agents can be suppressed, and a rubber composition having desired hardness and strength can be obtained.
  • the tire rubber composition produced in the present invention can be blended with carbon black and / or aroma oil together with silica and a silane coupling agent.
  • Examples of carbon black include furnace carbon black such as SAF, ISAF, HAF, FEF, GPF, HMF, and SRF, and these may be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area of carbon black is not particularly limited, but is preferably 70 to 240 m 2 / g, more preferably 90 to 200 m 2 / g. By setting the nitrogen adsorption specific surface area of carbon black to 70 m 2 / g or more, it is possible to ensure the mechanical properties and wear resistance of the rubber composition. Moreover, low rolling resistance can be made favorable by making the nitrogen adsorption specific surface area of carbon black into 240 m ⁇ 2 > / g or less. In the present specification, the nitrogen adsorption specific surface area of carbon black is measured according to JIS K6217-2.
  • Carbon black can be blended in an amount of preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the diene rubber.
  • By setting the blending amount of carbon black to 5 parts by mass or more mechanical properties and wear resistance of the rubber composition can be ensured.
  • low rolling resistance is securable by making the compounding quantity of carbon black into 100 mass parts or less.
  • the rubber composition for tires can contain fillers other than silica and carbon black.
  • fillers include calcium carbonate, magnesium carbonate, talc, clay, alumina, aluminum hydroxide, titanium oxide, and calcium sulfate. You may use these individually or in combination of 2 or more types.
  • an aromatic hydrocarbon having a mass percentage of 15% by mass or more obtained according to ASTM D2140 is preferably used. That is, it can contain aromatic hydrocarbons, paraffinic hydrocarbons, and naphthenic hydrocarbons in terms of its molecular structure, and the aromatic hydrocarbon content ratio is preferably 15% by mass or more, preferably 17% by mass. The above is more preferable.
  • the content ratio of the aromatic hydrocarbon in the aroma oil is preferably 70% by mass or less, more preferably 65% by mass or less.
  • Extract No. 4 S manufactured by Showa Shell Sekiyu Co., Ltd., AC-12, AC-460, AH-16, AH-24, AH-58 manufactured by Idemitsu Kosan Co., Ltd., and manufactured by Japan Energy Examples include process NC300S, process X-140, and the like.
  • the blending amount of the aroma oil is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the blending amount of the aroma oil is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the tire rubber composition produced in the present invention can contain a silica dispersant together with silica and a silane coupling agent.
  • examples of the dispersant for silica include amine compounds, silane compounds, epoxy compounds, guanidine compounds, and the like.
  • at least one selected from amine compounds, silane compounds, and guanidine compounds may be used.
  • amine compounds include cyclic amine compounds. Of these, cyclic amine compounds are preferred. Preferred examples of the cyclic amine compound include piperidine derivatives, piperazine derivatives, morpholine derivatives, thiomorpholine derivatives, and the like. Of these, piperazine derivatives, morpholine derivatives, and thiomorpholine derivatives are more preferable.
  • the cyclic amine compound may not have a silicon atom and an enamine structure (N—C ⁇ C).
  • Piperazine derivatives, morpholine derivatives, and thiomorpholine derivatives bind to the piperazine ring, morpholine ring, and thiomorpholine ring, respectively, and the carbon atom or nitrogen atom that forms the ring, either directly or via another organic group.
  • a structure having 3 to 30 carbon atoms is preferred.
  • the other organic group include divalent hydrocarbon groups containing oxygen such as a carbonyl group, an oxyalkylene group, and a polyoxyalkylene group.
  • hydrocarbon group having 3 to 30 carbon atoms examples include aliphatic hydrocarbon groups (including linear, branched and cyclic), aromatic hydrocarbon groups, and combinations thereof. Of these, an aliphatic hydrocarbon group is preferable and a saturated aliphatic hydrocarbon group is more preferable from the viewpoint of superior processability. From the viewpoint of superior workability, a hydrocarbon group having 8 to 22 carbon atoms is preferred.
  • the hydrocarbon group having 3 to 30 carbon atoms is preferably composed of only carbon atoms and hydrogen atoms.
  • the hydrocarbon group having 3 to 30 carbon atoms is preferably monovalent.
  • One molecule of the cyclic amine compound may have one or a plurality of hydrocarbon groups having 3 to 30 carbon atoms, and preferably one or two.
  • the piperazine-based derivative can be preferably represented by the following formula (I).
  • X 3 , X 4 , X 5 and X 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 3 to 30 carbon atoms, and X 1 and X 2 are independently from each other.
  • X 1 and X 2 are independently from each other.
  • At least one of X 2 is —A 1 —R 2 or —R 2 .
  • R 2 is a monovalent hydrocarbon group having 3 to 30 carbon atoms
  • a 1 is a carbonyl group or —R 4 (OH) —O—.
  • R 3 is a divalent hydrocarbon group having 2 to 3 carbon atoms
  • R 4 is a trivalent hydrocarbon group having 3 to 30 carbon atoms.
  • n is a number from 1 to 10, preferably from 1 to 5.
  • the monovalent hydrocarbon group having 3 to 30 carbon atoms is preferably a linear, branched or cyclic aliphatic hydrocarbon group.
  • examples of the sulfone-based protecting group include a methanesulfonyl group, a tosyl group, and a nosyl group.
  • examples of the carbamate protecting group include a tert-butoxycarbonyl group, an allyloxycarbonyl group, a benzyloxycarbonyl group, and a 9-fluorenylmethyloxycarbonyl group.
  • Examples of the piperazine derivatives include compounds represented by the following formula.
  • R independently represents -C 12 H 25 or -C 13 H 27 .
  • n is a number of 2 to 10, preferably 2 to 5.
  • R represents —C 12 H 25 or —C 13 H 27, and may be a mixture of these piperazine derivatives.
  • the morpholine derivative and the thiomorpholine derivative can be preferably represented by the following formula (II).
  • X 3 , X 4 , X 5 , and X 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 3 to 30 carbon atoms
  • X 1 is —A 1 —R 2 or —R 2
  • X 7 is an oxygen atom or a sulfur atom.
  • —R 2 is a monovalent hydrocarbon group having 3 to 30 carbon atoms
  • a 1 is a carbonyl group or —R 4 (OH) —O—
  • R 4 is 3 to 30 carbon atoms.
  • Valent hydrocarbon group In the above formula (II), the monovalent hydrocarbon group having 3 to 30 carbon atoms is preferably a linear, branched or cyclic aliphatic hydrocarbon group.
  • morpholine derivatives include compounds represented by the following formula.
  • R represents —C 12 H 25 or —C 13 H 27, and may be a mixture of these morpholine derivatives.
  • Examples of the thiomorpholine derivative include compounds in which the oxygen atom in the ring of the morpholine derivative is replaced with a sulfur atom.
  • the method for producing a cyclic amine compound comprising the piperazine derivative, morpholine derivative, or thiomorpholine derivative described above is not particularly limited, and can be obtained by an ordinary production method.
  • at least one selected from the group consisting of piperazine, morpholine and thiomorpholine which may have a substituent, a halogen atom (chlorine, bromine, iodine, etc.), an acid halogen group (an acid chloride group, an acid bromide group) , An acid iodide group, etc.) and a hydrocarbon compound having 3 to 30 carbon atoms and having at least one selected from the group consisting of glycidyloxy groups, if necessary, in a solvent. Can do.
  • the substituent is the same as described above.
  • the hydrocarbon group having 3 to 30 carbon atoms contained in the hydrocarbon compound is the same as described above.
  • Examples of the method for producing a piperazine derivative having a (poly) oxyalkyl group include a method of reacting a piperazine derivative having a hydroxy group and an alkylene oxide in the presence of a metal alkoxide.
  • the amount of the cyclic amine compound is preferably 0.5 parts by mass or more, more preferably 0.5 to 10 parts by mass, and still more preferably 0.8 parts by mass with respect to 100 parts by mass of the diene rubber. It is good that it is ⁇ 5 mass parts.
  • silane compound examples include alkylalkoxysilanes, and examples thereof include monoalkyltrialkoxysilanes, dialkyldialkoxysilanes, and trialkylmonoalkoxysilanes. Of these, alkyltrialkoxysilane is preferable, and alkyltriethoxysilane is more preferable.
  • alkylalkoxysilane By blending an alkylalkoxysilane, the aggregation of silica and the increase in viscosity of the rubber composition can be suppressed, and the wet grip performance can be further improved.
  • the alkyltriethoxysilane preferably has an alkyl group having 3 to 20 carbon atoms, more preferably an alkyl group having 7 to 20 carbon atoms.
  • an alkyl group having 3 to 20 carbon atoms propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group.
  • an alkyl group having 8 to 10 carbon atoms is more preferable, and an octyl group and a nonyl group are further preferable.
  • the compounding amount of alkyltriethoxysilane is preferably 0.5 to 10% by mass, more preferably 2 to 6% by mass, based on the silica compounding amount.
  • the compounding amount of the alkyltriethoxysilane is less than 0.5% by mass, the effect of suppressing the aggregation of silica and the effect of suppressing the increase in the viscosity of the rubber composition cannot be obtained sufficiently.
  • the compounding quantity of alkyl triethoxysilane exceeds 10 mass%, the residence to a roll will increase at the time of preparation of a rubber composition. In addition, the rolling resistance of the rubber composition may increase and the wear resistance may decrease.
  • the rubber composition for tires of the present invention is a rubber composition for tires such as a vulcanization or crosslinking agent, a vulcanization accelerator, an anti-aging agent, a plasticizer, a processing aid, a liquid polymer, a terpene resin, and a thermosetting resin.
  • Various additives generally used in the present invention can be blended within a range not impairing the object of the present invention. Such additives can be kneaded by a general method to form a rubber composition, which can be used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
  • tire rubber compositions 1 to 6 having the composition shown in Table 3 tire rubber compositions were produced by different production methods.
  • the rubber compositions prepared in the following Examples and Comparative Examples have the corresponding rubber composition formulations in Table 3 shown in the “Rubber Composition Formulation” column of Tables 1 and 2.
  • the compounding of the rubber composition in Table 3 describes the compounding amount with respect to 100 parts by mass of the diene rubber (SBR and / or modified SBR), and the abbreviation of each component and the mixing step of the first stage and the final stage are used in the mixer It was described whether it was input.
  • the total amount of each component described in the column of “First stage mixing” in Table 3 was transferred to a mixer (a closed banbury mixer with a capacity of 1.7 liters, manufactured by Kobe Steel Co., Ltd.). Were added and kneaded in the order of "first input”, “second input” and “third input” to obtain a kneaded product, which was discharged from the mixer and cooled. After cooling, the kneaded product was charged again into the mixer, and the components described in the column of “final stage mixing” in Table 3 were charged and mixed to prepare rubber compositions by 14 types of production methods ( Examples 1 to 10, standard examples, comparative examples 1 to 3).
  • the mixing of the Banbury mixer starts at a normal temperature (23 ° C.) with the temperature of each material set at 60 ° C.
  • Tables 1 and 2 show the mixing conditions of the first input component and the temperature after completion of mixing and the initial mixing temperature of the second input component as mixing conditions.
  • the mixing time of the second and third components was 1 minute each.
  • the kneaded product obtained in the first stage of mixing was cooled to 23 ° C. outside air cooling, and mixing after compounding the vulcanizing agent was carried out for 1.5 minutes with a Banbury mixer.
  • the obtained rubber composition for tire was vulcanized at 170 ° C. for 10 minutes using a mold having a predetermined shape (inner dimensions; length 150 mm, width 150 mm, thickness 2 mm) to prepare a vulcanized rubber test piece. .
  • a mold having a predetermined shape inner dimensions; length 150 mm, width 150 mm, thickness 2 mm
  • wet performance, rolling resistance and abrasion resistance were measured by the following test methods.
  • Abrasion resistance The obtained vulcanized rubber test piece was compliant with JIS K6264 using a Lambourne abrasion tester (manufactured by Iwamoto Seisakusho Co., Ltd.) at a temperature of 20 ° C., a load of 39 N, a slip rate of 30%, and a time of 4 minutes. The amount of wear was measured under the conditions. The obtained results are shown in the column of “Abrasion resistance” in Tables 1 and 2 as an index for setting the reciprocal number of the standard example to 100. Higher index means better wear resistance.
  • SBR styrene butadiene rubber (unmodified product), Nipol 1502 manufactured by Nippon Zeon Modified SBR: styrene butadiene rubber modified with an epoxy group, Nipol NS616 manufactured by Nippon Zeon ⁇ Silica: Rhodia 200MP, CTAB adsorption specific surface area of 203 m 2 / g
  • Surface treated silica Silica silane coupling agent obtained by surface treatment of 10 mass% of silica 69 by Rhodia 200MP and Si69 made by Evonik Degussa with respect to silica 1: Sulfide-based silane coupling agent, Si69 by Evonik Degussa, Bis (tri Ethoxysilylpropyl) tetrasulfide silane coupling agent 2: NXT silane manufactured by Momentive, represented by the following formula.
  • S -Zinc oxide 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.-Stearic acid: Stearic acid manufactured by NOF Corporation-Anti-aging agent 1: Santoflex 6PPD manufactured by Solutia Europe Anti-aging agent 2: PILNOX TDQ manufactured by Nocil Limited ⁇ Sulfur: Fine sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd. (sulfur content 95.24% by mass) ⁇ Vulcanization accelerator-1: Noxeller CZ-G (CZ) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. ⁇ Vulcanization accelerator-2: Soxinol DG (DPG) manufactured by Sumitomo Chemical Co., Ltd.
  • DPG Soxinol DG
  • the rubber compositions obtained by the production methods of Examples 1 to 10 had wet grip performance (tan ⁇ at 0 ° C.), low rolling resistance (tan ⁇ at 60 ° C.), and abrasion resistance. It was confirmed to improve.
  • the rubber composition obtained in Comparative Example 1 was blended with surface-treated silica instead of the silica in the standard example, but the rolling resistance cannot be improved due to the temperature rise of the mixer by the first charging.
  • the rubber composition obtained in Comparative Example 2 was blended with modified SBR instead of SBR in the standard example, but the balance of low rolling resistance and wet performance due to temperature rise of the mixer by the first input was Example 1. It is inferior to the rubber composition obtained in -5.
  • the first addition to the mixer in the first stage mixing the mixing was only silica, and the silane coupling agent was not added first. The ring agent does not react sufficiently and the wet performance and wear resistance performance cannot be improved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'une composition de caoutchouc pour un pneu ayant d'excellentes performances d'adhérence sur sol mouillé, une faible résistance au roulement, et une excellente résistance à l'usure. Le procédé de production d'une composition de caoutchouc contenant 80 à 180 parties en masse de silice par rapport à 100 parties en masse d'un caoutchouc à base de diène, et contenant un agent de couplage au silane en une quantité de 5 à 18 % en masse par rapport à la teneur en silice, le procédé étant caractérisé par l'introduction de la silice et de l'agent de couplage au silane dans un mélangeur, le mélange de la silice et de l'agent de couplage au silane, puis l'introduction du caoutchouc à base de diène dans le mélange et le malaxage du mélange obtenu.
PCT/JP2017/044086 2016-12-09 2017-12-07 Procédé de production d'une composition de caoutchouc pour pneu WO2018105707A1 (fr)

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WO2019107390A1 (fr) * 2017-11-28 2019-06-06 横浜ゴム株式会社 Pneu et procédé de fabrication de composition de caoutchouc pour pneu utilisé dans celui-ci
JP2019099589A (ja) * 2017-11-28 2019-06-24 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP2019182986A (ja) * 2018-04-09 2019-10-24 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP2019196418A (ja) * 2018-05-07 2019-11-14 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法

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JP2001011245A (ja) * 1999-07-02 2001-01-16 Sumitomo Rubber Ind Ltd トレッド用ゴム組成物
JP2002003652A (ja) * 2000-06-20 2002-01-09 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2012007068A (ja) * 2010-06-24 2012-01-12 Yokohama Rubber Co Ltd:The スタッドレスタイヤ用ゴム組成物およびこれを用いるスタッドレスタイヤ
JP2013245306A (ja) * 2012-05-28 2013-12-09 Bridgestone Corp タイヤ
JP2016191018A (ja) * 2015-03-31 2016-11-10 東洋ゴム工業株式会社 ゴム組成物の製造方法、ゴム組成物および空気入りタイヤ

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EP2623551B1 (fr) * 2010-10-01 2019-07-24 Bridgestone Corporation Procédé de fabrication d'une composition de caoutchouc
CN103524796B (zh) * 2012-07-04 2015-08-19 中国石油天然气股份有限公司 一种用于轮胎胎面的橡胶组合物及其制备方法
CN105246963B (zh) * 2013-02-25 2017-11-21 横滨橡胶株式会社 轮胎胎面用橡胶组合物及使用其的充气轮胎

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JP2001011245A (ja) * 1999-07-02 2001-01-16 Sumitomo Rubber Ind Ltd トレッド用ゴム組成物
JP2002003652A (ja) * 2000-06-20 2002-01-09 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2012007068A (ja) * 2010-06-24 2012-01-12 Yokohama Rubber Co Ltd:The スタッドレスタイヤ用ゴム組成物およびこれを用いるスタッドレスタイヤ
JP2013245306A (ja) * 2012-05-28 2013-12-09 Bridgestone Corp タイヤ
JP2016191018A (ja) * 2015-03-31 2016-11-10 東洋ゴム工業株式会社 ゴム組成物の製造方法、ゴム組成物および空気入りタイヤ

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019107390A1 (fr) * 2017-11-28 2019-06-06 横浜ゴム株式会社 Pneu et procédé de fabrication de composition de caoutchouc pour pneu utilisé dans celui-ci
JP2019099589A (ja) * 2017-11-28 2019-06-24 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP2019182986A (ja) * 2018-04-09 2019-10-24 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP7127340B2 (ja) 2018-04-09 2022-08-30 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP2019196418A (ja) * 2018-05-07 2019-11-14 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法

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