Patent Application
20250230301
The present invention pertains to a rubber composition for heavy-load tires which can provide a cross-linked rubber having remarkably reduced heat buildup and having high wear resistance and high chipping resistance, and can be suitably used in applications to heavy-load tires.
An important feature for heavy-load tires for use as truck and bus tires and the like is excellent wear resistance and chipping resistance that enable the tires to have a longer lifespan. On the other hand, recent environmental and resource issues have created a growing demand for low heat buildup (high fuel efficiency). In order to achieve a heavy-load tire imparted with low heat buildup, addition of silica to a composition for heavy-load tires has been studied. Unfortunately, this ends up with reduced wear resistance.
For example, Patent Document 1 discloses a rubber composition for heavy-load tires comprising 40 to 60 parts by mass of silica having a CTAB adsorption specific surface area of 180 to 300 m/g and 3 to 10 parts by mass of carbon black having a nitrogen adsorption specific surface area of 110 to 150 m/g relative to 100 parts by mass of a rubber component composed of 55 to 70% by mass of natural rubber and 30 to 45% by mass of butadiene rubber, and containing 6 to 15% by mass of a silane coupling agent having a sulfide bond relative to the amount of the silica.
Recently, demands for low heat buildup, wear resistance, and chipping resistance of heavy-load tires have been increasing. However, the technique disclosed in Patent Document 1 does not meet high requirements of low heat buildup, wear resistance, and chipping resistance. For this reason, a further improvement in low heat buildup, wear resistance, and chipping resistance has been demanded from the viewpoint of suitable use in applications to heavy-load tires.
The present invention has been made in consideration of such circumstances. An object of the present invention is to provide a rubber composition for heavy-load tires which can provide a cross-linked rubber having remarkably reduced heat buildup, high wear resistance, and high chipping resistance.
The present inventors, who have conducted extensive research to achieve the above object, have found that the above object can be achieved by a rubber composition prepared by combining a conjugated diene polymer and silica, the conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica, and have completed the present invention.
Specifically, the present invention provides a rubber composition for heavy-load tires comprising a conjugated diene polymer and silica, the conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica.
In the rubber composition for heavy-load tires according to the present invention, preferably, the vinyl bond content in a conjugated diene monomer unit constituting the conjugated diene polymer is 5 to 40% by weight.
In the rubber composition for heavy-load tires according to the present invention, preferably, the silica has a nitrogen adsorption specific surface area determined by the BET method of 30 to 500 m2/g.
In the rubber composition for heavy-load tires according to the present invention, preferably, the amount of the silica present is 10 to 200 parts by weight relative to 100 parts by weight of rubber components containing the conjugated diene polymer.
The rubber composition for heavy-load tires according to the present invention preferably further comprises carbon black. In this case, more preferably, the carbon black has a nitrogen adsorption specific surface area determined by the BET method of 30 m2/g or more. More preferably, the amount of the carbon black present is 10 to 200 parts by weight relative to 100 parts by weight of the rubber components containing the conjugated diene polymer.
In the rubber composition for heavy-load tires according to the present invention, preferably, the amount of the conjugated diene polymer present is 10 to 80% by weight in 100% by weight of the total rubber components.
Preferably, the rubber composition for heavy-load tires according to the present invention further comprises a natural rubber, wherein the amount of the natural rubber present is 10 to 80% by weight in 100% by weight of the total rubber components.
In the rubber composition for heavy-load tires according to the present invention, preferably, the functional group interactive with silica in the conjugated diene polymer is a group having a structure represented by Si—ORa (where Ra is a hydrogen atom or an optionally substituted hydrocarbyl group).
Preferably, the rubber composition for heavy-load tires according to the present invention further comprises a silane coupling agent.
Preferably, the rubber composition for heavy-load tires according to the present invention further comprises a cross-linking agent.
The present invention also provides a cross-linked rubber obtained by cross-linking the rubber composition for heavy-load tires according to the present invention.
Furthermore, the present invention provides a heavy-load tire comprising the cross-linked rubber according to the present invention.
The present invention provides a rubber composition for heavy-load tires which can provide a cross-linked rubber having remarkably reduced heat buildup and excellent wear resistance high chipping resistance.
The rubber composition for heavy-load tires according to the present invention comprises a conjugated diene polymer and silica, the conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica.
The conjugated diene polymer used in the present invention is a polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica. In the present invention, the conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica described later is used in combination with silica, and therefore a cross-linked rubber having reduced heat buildup and excellent wear resistance and chipping resistance can be obtained.
The conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica (hereinafter, appropriately referred to as “conjugated diene polymer”) used in the present invention is mainly composed of a conjugated diene monomer unit, and has a functional group interactive with silica.
The content of the conjugated diene monomer unit in the total monomer units constituting the conjugated diene polymer used in the present invention is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 998 by weight or more, particularly preferably 99.7% by weight or more. When the content of the conjugated diene monomer unit falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Examples of conjugated diene compounds forming the conjugated diene monomer unit include, but should not be limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and the like. Among these, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred. These conjugated diene compounds may be used alone or in combination.
The conjugated diene polymer used in the present invention preferably contains 1,3-butadiene units as the conjugated diene monomer unit, and more preferably contains 1,3-butadiene units and isoprene units.
When the conjugated diene polymer used in the present invention contains 1,3-butadiene units and isoprene units, the proportion of the content of 1,3-butadiene units and that of the isoprene units in the total monomer units constituting the conjugated diene polymer is not particularly limited, but the proportion of the weight of isoprene units to that of 1,3-butadiene units is preferably 0.001 to 0.2, more preferably 0.005 to 0.1, particularly preferably 0.01 to 0.05. When the proportion of the content of 1,3-butadiene units and that of the isoprene units falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The conjugated diene polymer used in the present invention may further contain an additional monomer unit other than the conjugated diene monomer unit. Examples of additional monomers constituting such additional monomer units include aromatic vinyl monomers such as styrene, methylstyrene, ethylstyrene, t-butylstyrene, «-methylstyrene, «-methyl-p-methylstyrene, chlorostyrene, bromostyrene, methoxystyrene, dimethylaminomethylstyrene, dimethylaminoethylstyrene, diethylaminomethylstyrene, diethylaminoethylstyrene, cyanoethylstyrene, and vinylnaphthalene; linear olefin compounds such as ethylene, propylene, and 1-butene; cyclic olefin compounds such as cyclopentene and 2-norbornene; non-conjugated diene compounds such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene; and the like. Among these, aromatic vinyl monomers are preferred, and styrene is more preferred. These additional monomers may be used alone or in combination.
The content of the additional monomer unit in the total monomer units constituting the conjugated diene polymer used in the present invention is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 18 by weight or less, particularly preferably 0.3% by weight or less.
When the conjugated diene polymer used in the present invention contains the additional monomer unit, the lower limit of the content of the additional monomer unit in the total monomer units constituting the conjugated diene polymer used in the present invention is not particularly limited, but can be 0.01% by weight or more, for example. and the upper limit of the content of the conjugated diene monomer unit is not particularly limited, but can be 99.99% by weight or less, for example. When the contents of the monomer units fall within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The conjugated diene polymer used in the present invention has a glass transition temperature (Tg) of −60° C. or lower, and the glass transition temperature (Tg) is not particularly limited. The glass transition temperature (Tg) is preferably −100 to −67° C., more preferably −97 to −74° C., still more preferably −95 to −81° C., particularly preferably −93 to −88° C. When the glass transition temperature (Tg) falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained. The glass transition temperature (Tg) of the conjugated diene polymer can be controlled within the above ranges by any method, and examples thereof include a method of controlling the vinyl bond content of the conjugated diene monomer unit constituting the conjugated diene polymer, a method of controlling the weight average molecular weight of the conjugated diene polymer, and the like.
The vinyl bond content of the conjugated diene monomer unit constituting the conjugated diene polymer used in the present invention is preferably 5 to 40% by weight, more preferably 7 to 33% by weight, still more preferably 9 to 25% by weight, particularly preferably 11 to 20% by weight, most preferably 12 to 15% by weight. When the vinyl bond content falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The conjugated diene polymer used in the present invention is preferably polymerized using a polymerization initiator containing an organic alkali metal compound as a primary catalyst, more preferably polymerized using an organic monolithium compound as a polymerization initiator, and still more preferably polymerized using n-butyllithium as a polymerization initiator. By using a conjugated diene polymer polymerized using the above-mentioned polymerization initiator, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The conjugated diene polymer used in the present invention has a functional group interactive with silica in the polymer. The functional group interactive with silica refers to a functional group capable of forming a covalent bond with the surface of silica, or creating an intermolecular force (e.g., ion-dipole interaction, dipole-dipole interaction, hydrogen bond, or van der Waals force) weaker than a covalent bond. Examples of such functional groups interactive with silica include, but are not particularly limited to, nitrogen atom-containing functional groups, silicon atom-containing functional groups, oxygen atom-containing functional groups, and the like. Among these, preferred are silicon atom-containing functional groups, and preferred are groups having a structure represented by Si—ORa (wherein Ra is a hydrogen atom or a hydrocarbyl group optionally having a substituent) because they are more interactive with silica.
Examples of hydrocarbyl groups which can form Ra include alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, and the like. Preferred are alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and the like. Among these, more preferred are a methyl group and an ethyl group, and particularly preferred is a methyl group. Examples of hydrocarbyl groups having a substituent include hydrocarbyl groups having a hydrocarbyloxy group as a substituent, and the like, and examples of hydrocarbyl groups having a hydrocarbyloxy group as a substituent include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group; and aryloxyalkyl groups such as a phenoxymethyl group; and the like.
Examples of methods of introducing the functional group interactive with silica to the conjugated diene polymer used in the present invention include, but should not be limited to, a method for producing the conjugated diene polymer in which monomers including the conjugated diene compound are polymerized to yield a conjugated diene polymer chain having an active end, and the conjugated diene polymer chain having an active end is reacted with a modifier having a functional group interactive with silica, and the like.
The weight average molecular weight (Mw) of the conjugated diene polymer used in the present invention is preferably 150,000 to 3,000,000, more preferably 250,000 to 1,000,000, still more preferably 350,000 to 700,000, further still more preferably 400,000 to 550,000, particularly preferably 430,000 to 500,000, most preferably 450,000 to 480,000. When the weight average molecular weight (Mw) of the conjugated diene polymer falls within the above ranges, compounding of silica with the conjugated diene polymer is facilitated to further enhance the processability of the rubber composition, and further, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The molecular weight distribution, which is represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the conjugated diene polymer used in the present invention to the number average molecular weight (Mn) thereof, is preferably 1.1 to 3.5, more preferably 1.2 to 3.0, still more preferably 1.3 to 2.5, particularly preferably 1.4 to 2.0. When the molecular weight distribution (Mw/Mn) of the conjugated diene polymer used in the present invention falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained. The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined as polystyrene-equivalent values determined by gel permeation chromatography.
The conjugated diene polymer used in the present invention has a Mooney viscosity (ML1+4, 100° C.) of preferably 20 to 100, more preferably 35 to 90, still more preferably 45 to 80, particularly preferably 50 to 70, most preferably 55 to 65. When the conjugated diene polymer is recovered as an oil extended rubber, the Mooney viscosity of the oil extended rubber is preferably controlled to fall within the above ranges.
Although the content of the conjugated diene polymer having a glass transition temperature (To) of −60° C. or lower and having the functional group interactive with silica in the rubber composition for heavy-load tires according to the present invention is not particularly limited, the content thereof in 100% by weight of the total rubber components contained in the rubber composition for heavy-load tires according to the present invention is preferably 10 to 80% by weight, more preferably 12 to 60% by weight, still more preferably 15 to 40% by weight. When the content of the conjugated diene polymer falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Although the conjugated diene polymer used in the present invention can be produced by any method without limitation, suitable is a method for producing a conjugated diene polymer, comprising:
The above-mentioned monomers can be used in the polymerization step as the monomers including a conjugated diene compound.
The inert solvent used in polymerization may be one generally used in solution polymerization, and is not particularly limited as long as it does not inhibit the polymerization reaction. Specific examples of such insert solvents include chain aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ether compounds such as tetrahydrofuran and diethyl ether; and the like. These inert solvents may be used alone or in combination of two or more. Although not particularly limited, the amount of the inert solvent used is selected to provide a monomer concentration of, for example, 1 to 50% by weight, preferably 10 to 40% by weight.
The polymerization initiator used in polymerization is not particularly limited as long as the monomers including the conjugated diene compound are polymerized to yield a conjugated diene polymer chain having an active end. Specific examples thereof include organic alkali metal compounds, organic alkaline earth metal compounds, and polymerization initiators having a lanthanide-series metal compound or the like as a primary catalyst. Examples of organic alkali metal compounds include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; organic polyvalent lithium compounds such as dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, and 1,3,5-tris(lithiomethyl)benzene; organic sodium compounds such as sodium naphthalene; organic potassium compounds such as potassium naphthalene; and the like. Examples of organic alkaline earth metal compounds include di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, di-t-butoxystrontium, diethoxybarium, diisopropoxybarium, diethylmercaptobarium, di-t-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, diketylbarium, and the like. Examples of polymerization initiators containing a lanthanide-series metal compound as a primary catalyst include polymerization initiators containing a lanthanide-series metal salt of a lanthanide-series metal, such as lanthanum, cerium, praseodymium, neodymium, samarium, or gadolinium, and a carboxylic acid, a phosphorus-containing organic acid, or the like as a primary catalyst, and a promoter such as an alkylaluminum compound, an organoaluminum hydride compound, or an organoaluminum halide compound. Among these polymerization initiators, organic monolithium compounds and organic poly-lithium compounds are preferably used, organic monolithium compounds are more preferably used, and n-butyllithium is particularly preferably used.
The organic alkali metal compounds may be reacted in advance with a secondary amine compound, such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, piperidine, hexamethyleneimine, or heptamethyleneimine, and used as organic alkali metal amide compounds. These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator used can be selected according to the molecular weight of the target conjugated diene polymer chain, and is in the range of usually 1 to 50 mmol, preferably 1.5 to 20 mmol, more preferably 2 to 15 mmol per 1000 g of monomers.
The polymerization temperature is in the range of typically-80 to +150° C., preferably 0 to 100° C., more preferably from 30 to 90° C. The polymerization mode can be any of a batch mode and a continuous mode.
In the polymerization step, preferably, the monomers including the conjugated diene compound are polymerized in the presence of a polar compound. Specifically, a polar compound is used in an amount of preferably 0.01 to 1.2 mol, more preferably 0.1 to 1.1 mol, still more preferably 0.1 to 1.0 mol per mol of the polymerization initiator. Such use of a polar compound in the polymerization enables suitable control of the vinyl bond content of conjugated diene monomer units in the conjugated diene polymer chain formed in the polymerization step within the above ranges.
The polymerization in the presence of a polar compound may be performed by any method without limitation, and examples thereof include methods such as performing polymerization in an inert solvent for polymerization containing the polar compound. Specific examples of the polar compound include ether compounds such as dibutylether, tetrahydrofuran, and 2,2-di(tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine; alkali metal alkoxides; phosphine compounds; and the like. Among these, preferred are ether compounds and tertiary amines, more preferred are tertiary amines, and particularly preferred is tetramethylethylenediamine. These polar compounds may be used alone or in combination.
Although the weight average molecular weight (Mw) of the conjugated diene polymer chain having an active end obtained in the polymerization step is not particularly limited, the polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography is preferably 150,000 to 3,000,000, more preferably 170,000 to 2,000,000, still more preferably 200,000 to 1500,000, particularly preferably 350,000 to 650,000, most preferably 380,000 to 520,000. When the weight average molecular weight (Mw) of the conjugated diene polymer chain having an active end falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Although the molecular weight distribution, which is represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the conjugated diene polymer chain having an active end obtained in the polymerization step to the number average molecular weight (Mn) thereof, is not particularly limited, the molecular weight distribution is preferably 1.1 to 3.5, more preferably 1.2 to 3.0, still more preferably 1.3 to 2.5. When the molecular weight distribution (Mw/Mn) of the conjugated diene polymer chain having an active end falls within the above ranges, production of the conjugated diene polymer is facilitated.
In the present invention, in order to obtain a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level, the polymerization step may be a step below.
Specifically, the polymerization step includes a step of polymerizing monomers including isoprene or isoprene and an aromatic vinyl compound in an inert solvent using a polymerization initiator to provide a polymer block (A) having an active end containing 80 to 100% by weight of isoprene monomer units and 0 to 20% by weight of aromatic vinyl monomer units; and
When such steps are employed, the conjugated diene polymer chain having an active end obtained in the polymerization step can be formed of the polymer block (A) containing 80 to 100% by weight of isoprene monomer units and 0 to 20% by weight of aromatic vinyl monomer units and the polymer block (B) containing 1,3-butadiene monomer units in which the polymer block (A) and the polymer block (B) are serially linked to each other.
The following description illustrates such an embodiment.
It is sufficient that the polymer block (A) in the conjugated diene polymer chain according to one embodiment of the present invention contains 80 to 100% by weight of isoprene monomer units and 0 to 20% by weight of the aromatic vinyl monomer units in the polymer block (A). The polymer block (A) contains preferably 85 to 97% by weight of isoprene monomer units and 3 to 15% by weight of aromatic vinyl monomer units, more preferably 89 to 95% by weight of isoprene monomer units and 5 to 11% by weight of aromatic vinyl monomer units. When the proportion of the content of the isoprene monomer units and that of the aromatic vinyl monomer units falls within the above ranges, the compatibility of the conjugated diene polymer with silica can be further enhanced, and thereby, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Examples of aromatic vinyl compounds which can be used to form aromatic vinyl monomer units in the polymer block (A) are the same aromatic vinyl compounds listed above. Among these, preferred is styrene. These aromatic vinyl compounds may be used alone or in combination.
Although the polymer block (A) preferably consists only of isoprene monomer units or isoprene monomer units and aromatic vinyl monomer units, additional monomer units may be present as needed in addition to isoprene monomer units or isoprene monomer units and aromatic vinyl monomer units. Examples of additional compounds which can be used to form such additional monomer units include conjugated diene compounds other than isoprene, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene; «, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids or acid anhydrides such as acrylic acid, methacrylic acid, and maleic anhydride; unsaturated carboxylic acid esters such as methyl methacrylate, ethyl acrylate, and butyl acrylate; unconjugated dienes such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene; and the like. Among these, preferred is 1,3-butadiene. These additional monomers may be used alone or in combination of two or more. The content of additional monomer units in the polymer block (A) is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 6% by weight or less.
In the present invention, the polymer block (A) in the conjugated diene polymer chain is formed by polymerizing the monomers including isoprene or isoprene and an aromatic vinyl compound in an inert solvent using a polymerization initiator. The polymer block (A) formed has an active end.
Examples of inert solvents which can be used in polymerization of the monomers including isoprene or isoprene and the aromatic vinyl compound to form the polymer block (A) are the same inert solvents listed above. The amount of the inert solvent used is selected to provide a monomer concentration of preferably 1 to 80% by weight, more preferably 10 to 50% by weight.
Any polymerization initiator can be used without limitation to form the polymer block (A) as long as the monomers including isoprene or isoprene and the aromatic vinyl compound are polymerized to provide a polymer chain having an active end. Specific examples thereof are the same polymerization initiators listed above.
The amount of the polymerization initiator used can be selected according to the desired molecular weight, and is preferably 4 to 250 mmol, more preferably 6 to 200 mmol, particularly preferably 10 to 70 mmol per 100 g of the monomers including isoprene or isoprene and the aromatic vinyl compound.
The polymerization temperature in polymerization of the monomers including isoprene or isoprene and the aromatic vinyl compound is preferably −80 to +150° C., more preferably 0 to 100° C., still more preferably 20 to 90° C. The polymerization mode may be any mode such as a batch or continuous mode. The bonding form may be any of various bonding forms such as block, tapered, and random forms.
The polymer block (A) is preferably formed by polymerizing the monomers including isoprene or isoprene and the aromatic vinyl compound in the presence of a polar compound. Specifically, a polar compound is used in an amount of preferably 0.01 to 100 mol, more preferably 0.03 to 30 mol, still more preferably 0.05 to 1 mol per mol of the polymerization initiator. Such use of a polar compound in the polymerization enables suitable control of the vinyl bond content of isoprene monomer units in the polymer block (A). The vinyl bonds in isoprene units may be either in the 1,2-vinyl form or in the 3,4-vinyl form.
Examples of methods for polymerizing the monomers including isoprene or isoprene and the aromatic vinyl compound in the presence of a polar compound include, but are not particularly limited to, methods such as performing polymerization in an inert solvent for polymerization containing the polar compound. Examples of usable polar compounds are the same polar compounds listed above.
The vinyl bond content in the isoprene monomer units of the polymer block (A) is preferably 1 to 90% by weight, more preferably 2 to 50% by weight, still more preferably 3 to 30% by weight, particularly preferably 4 to 20% by weight, most preferably 5 to 10% by weight. When the vinyl bond content in the isoprene monomer units falls within the above ranges, a cross-linked rubber having further reduced heat buildup can be obtained. In this specification, the vinyl bond content in the isoprene monomer units refers to the proportion of the total amount of isoprene monomer units having a 1,2-structure and isoprene monomer units having a 3,4-structure in the isoprene monomer units.
The weight average molecular weight (Mw) of the polymer block (A) is preferably 500 to 15,000, more preferably 1,000 to 12,000, particularly preferably 1,500 to 10,000 as polystyrene-equivalent values determined by gel permeation chromatography. When the weight average molecular weight of the polymer block (A) falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The molecular weight distribution, which is represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of the polymer block (A) is preferably 1.0 to 1.5, more preferably 1.0 to 1.3. When the molecular weight distribution (Mw/Mn) of the polymer block (A) falls within the above ranges, production of the conjugated diene polymer can be further facilitated.
The conjugated diene polymer chain according to one embodiment of the present invention contains preferably 95% by weight or more of 1,3-butadiene monomer units, more preferably 99% by weight or more of 1,3-butadiene monomer units, still more preferably 100% by weight of 1,3-butadiene monomer units in the polymer block (B). When the content of the 1,3-butadiene monomer units falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The polymer block (B) may contain an additional monomer unit as desired in addition to the 1,3-butadiene monomer units. Examples of additional monomers which can be used to form additional monomer units are the same compounds as those listed in the polymer block (A) (excluding 1,3-butadiene). In the polymer block (B), isoprene can also be used as an additional monomer. The content of the additional monomer unit in the polymer block (B) is preferably 5% by weight or less, more preferably 1% by weight or less.
In one embodiment of the present invention, the polymer block (B) in the conjugated diene polymer chain and the polymer block (A) are formed to be serially linked to each other, by mixing the polymer block (A) having an active end and the monomers including 1,3-butadiene, and continuing the polymerization reaction. The polymer block (B) formed has an active end. On the other hand, the polymer block (A) loses the active end.
In the polymerization of the polymer block (A) and the monomers including 1,3-butadiene to form the polymer block (B), any inert solvent may be used without limitation, and any of the same inert solvents listed above can be used.
The amount of the polymer block (A) having an active end used in formation of the polymer block (B) may be selected according to the desired molecular weight, and is in the range of preferably 0.1 to 5 mmol, more preferably 0.15 to 2 mmol, still more preferably 0.2 to 1.5 mmol per 100 g of the monomers including 1,3-butadiene.
The polymer block (A) and the monomers including 1,3-butadiene may be mixed by any method without limitation. The polymer block (A) having an active end may be added to a solution of the monomers including 1,3-butadiene, or the monomers including 1,3-butadiene may be added to a solution of the polymer block (A) having an active end. From the viewpoint of control of polymerization, a preferred method is adding the polymer block (A) having an active end to a solution of the monomers including 1,3-butadiene.
The polymerization temperature in polymerization of the monomers including 1,3-butadiene is in the range of preferably −80 to +150° C., more preferably 0 to 100° C., still more preferably 20 to 90° C. The polymerization mode may be any mode such as a batch or continuous mode.
In one embodiment of the present invention, the polymer block (B) is preferably formed in the same manner as that in formation of the polymer block (A), and the monomers including 1,3-butadiene are polymerized in the presence of a polar compound. Specifically, a polar compound is used in an amount of preferably 0.01 to 0.50 mol, more preferably 0.05 to 0.40 mol, still more preferably 0.08 to 0.35 mol per mol of the polymerization initiator. Such use of a polar compound in the polymerization enables suitable control of the vinyl bond content of 1,3-butadiene monomer units in the polymer block (B). As a result, the vinyl bond content of conjugated diene monomer units in the conjugated diene polymer finally obtained can be suitably controlled within the ranges described above.
The polymerization of the monomers including 1,3-butadiene in the presence of a polar compound may be performed by any method without limitation. Examples thereof include methods such as performing polymerization in an insert solution containing the polymer compound. In this method, the polar compound is added such that the total of the amount of the polar compound added to form the polymer block (A) and the amount of the polar compound additionally added falls within the ranges described above. For this reason, when the polymer block (A) is formed in the presence of an amount of the polar compound sufficient to control the vinyl bond content of 1,3-butadiene monomer units in the polymer block (B), further addition of the polar compound is not needed. The polar compound may be any of the same polar compounds listed above.
Thus, a conjugated diene polymer chain containing the polymer block (A) and the polymer block (B) and having an active end can be obtained. In one embodiment of the present invention, although from the viewpoint of productivity, it is preferable that the conjugated diene polymer chain having an active end consist of a polymer block (A)-polymer block (B) chain, and the polymer block (B) have an active end, two or more polymer blocks (A) may be present, and an additional polymer block may be present. Examples of such conjugated diene polymer chains having an active end include conjugated diene polymer chains having an active end such as polymer block (A)-polymer block (B)-polymer block (A), and the like. In this case, an active end is formed at the end of the polymer block (A) formed after the polymer block (B). In the case where the polymer block (A) is formed on the active end side of the conjugated diene polymer chain, the amount of isoprene used is preferably 10 to 100 mol, more preferably 15 to 70 mol, particularly preferably 20 to 35 mol per mol of the polymerization initiator used in the first polymerization reaction (polymerization reaction to form the first polymer block (A)).
The weight ratio of the polymer block (A) to the polymer block (B) (weight of polymer block (A)/weight of polymer block (B)) of the conjugated diene polymer chain having an active end obtained in one embodiment of the present invention (in the case where multiple polymer blocks (A) and multiple polymer blocks (B) are present, the weight ratio based on the total weights thereof) is preferably 0.001 to 0.2, more preferably 0.005 to 0.1, particularly preferably 0.01 to 0.05. When the weight ratio of the polymer block (A) to the polymer block (B) falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Next, in the modification step, the conjugated diene polymer chain having an active end obtained in the polymerization step described above is reacted with a modifier having a functional group interactive with silica.
The modifier having a functional group interactive with silica used in the modification step is not particularly limited, and may be any compound which is reactive with the conjugated diene polymer chain having an active end obtained in the polymerization step described above and has a functional group interactive with silica. Examples of the functional group interactive with silica include, but are not particularly limited to, nitrogen atom-containing functional groups, silicon atom-containing functional groups, oxygen atom-containing functional groups, and the like. Among these, preferred are silicon atom-containing functional groups, and preferred are groups having a structure represented by Si—ORa (wherein Ra is a hydrogen atom or a hydrocarbyl group optionally having a substituent) because they are more interactive with silica.
Suitable modifiers having such a functional group interactive with silica for use in the present invention are siloxane compounds. Such siloxane compounds may be any compounds without limitation as long as they have the structure represented by (—Si—O—Si—). Preferred are organosiloxanes having an organic group in addition to the structure represented by (—Si—O—Si—), and more preferred are polyorganosiloxanes represented by General Formula (1) below.
In General Formula (1), R1 to R8 are alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 12 carbon atoms, which may be the same or different from each other; X1 and X4 are any groups selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and epoxy group-containing groups having 4 to 12 carbon atoms, which may be the same or different from each other; X2 is an alkoxy group having 1 to 5 carbon atoms or an epoxy group-containing group having 4 to 12 carbon atoms, and if multiple X2s are present, they may be the same or different from each other; X3 is a group containing 2 to 20 repeating units of an alkylene glycol, and if multiple X3s are present, they may be the same or different from each other; “m” is an integer of 1 to 200, “n” is an integer of 0 to 200, “k” is an integer of 0 to 200, and “m+n+k” is 1 or more.
For the polyorganosiloxanes represented by General Formula (1), examples of alkyl groups having 1 to 6 carbon atoms which may form R1 to R3, X1, and X4 in General Formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and the like. Examples of aryl groups having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, and the like. Among these, preferred are a methyl group and an ethyl group because of ease of production of these polyorganosiloxanes themselves.
Examples of alkoxy groups having 1 to 5 carbon atoms which may form X1 X2, and X4 in the polyorganosiloxanes represented by General Formula (1) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and the like. Among these, preferred are a methoxy group and an ethoxy group because of ease of production of these polyorganosiloxanes themselves.
Examples of epoxy group-containing group having 4 to 12 carbon atoms which may form X1 X2, and X4 in the polyorganosiloxanes represented by General Formula (1) include groups represented by General Formula (2):
—Z3—Z4-E2 (2)
In General Formula (2), Z3 is an alkylene or alkylarylene group having 1 to 10 carbon atoms, Z4 is a methylene group, a sulfur atom, or an oxygen atom, and E2 is an epoxy group-containing hydrocarbon group having 2 to 10 carbon atoms.
Preferred groups represented by General Formula (2) are those wherein Z4 is an oxygen atom, more preferred groups are those wherein Z4 is an oxygen atom and E2 is a glycidyl group, and particularly preferred groups are those wherein Z3 is an alkylene group having 1 to 3 carbon atoms, Z4 is an oxygen atom, and E2 is a glycidyl group.
In the polyorganosiloxanes represented by General Formula (1), X1 and X4 are each preferably an epoxy group-containing group having 4 to 12 carbon atoms or an alkyl group having 1 to 6 carbon atoms among those listed above. X2 is preferably an epoxy group-containing group having 4 to 12 carbon atoms among those listed above. More preferably, X1 and X4 are each an alkyl group having 1 to 6 carbon atoms, and X2 is an epoxy group-containing group having 4 to 12 carbon atoms.
In the organosiloxanes represented by General Formula (1), preferred groups for X3, that is, preferred groups containing 2 to 20 repeating units of an alkylene glycol are groups represented by General Formula (3) below:
In General Formula (3), “t” is an integer of 2 to 20, X5 is an alkylene or alkylarylene group having 2 to 10 carbon atoms, R9 is a hydrogen atom or a methyl group, and X6 is an alkoxy or aryloxy group having 1 to 10 carbon atoms. Among these, preferred are those wherein “t” is an integer of 2 to 8, X5 is an alkylene group having 3 carbon atoms, R9 is a hydrogen atom, and X6 is a methoxy group.
In the polyorganosiloxanes represented by General Formula (1), “m” is an integer of 1 to 200, preferably an integer of 20 to 150, more preferably an integer of 30 to 120. When “m” is 1 or more, the coupling ratio is readily controlled within a suitable range described later. As a result, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained. Moreover, when “m” is 200 or less, such polyorganosiloxanes represented by General Formula (1) themselves can be easily produced, and are also easier to handle because their viscosity is not too high.
In the polyorganosiloxanes represented by General Formula (1), “n” is an integer of 0 to 200, preferably an integer of 0 to 150, more preferably an integer of 0 to 120, and “k” is an integer of 0 to 200, preferably an integer of 0 to 150, more preferably an integer of 0 to 130. The total number of “m”, “n”, and “k” is 1 or more, preferably 3 to 400, more preferably 20 to 300, particularly preferably 30 to 250. When the total number of “m”, “n”, and “k” is 1 or more, the reaction of such a polyorganosiloxane represented by General Formula (1) and the conjugated diene copolymer chain having an active end easily proceeds, and when the total number of “m”, “n”, and “k” is 400 or less, such polyorganosiloxanes represented by General Formula (1) themselves can be easily produced, and are also easier to handle because their viscosity is not too high.
The amount of the siloxane compound in the modification step is preferably 0.1 mol or more, more preferably 0.2 mol or more, still more preferably 0.5 mol or more, particularly preferably 1.0 mol or more, most preferably, 1.1 mol or more, and preferably 10 mol or less, more preferably 5 mol or less, still more preferably 2.5 mol or less, particularly preferably 2 mol or less based on the number of (—Si—O—) repeating units in the siloxane compound per mol of the polymerization initiator used in the polymerization in the polymerization step described above. When the amount of the siloxane compound used falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Especially, the amount of the siloxane compound used is particularly preferably 1 mol or more based on the number of (—Si—O—) repeating units per mol of the polymerization initiator because such an amount enables the active ends of the conjugated diene polymer chains having an active end obtained in the polymerization step to almost completely react with the siloxane compound. Specifically, an alkyl metal group, that is, a group represented by —R-M+ (where R is a hydrocarbon group forming the polymer chain end, and M is an alkali metal atom, an alkaline earth metal atom, or a lanthanide-series metal atom) as the active end of the conjugated diene polymer chain having an active end obtained in the polymerization step can be almost completely consumed.
The siloxane compound may be reacted with the conjugated diene polymer chain having an active end by any method without limitation. Examples thereof include methods such as mixing the substances in a solvent capable of dissolving them. In this method, as the solvent, any of those listed as inert solvents for the polymerization step described above or the like may be used. Moreover, in this method, a preferable and simple process is adding the siloxane compound to the polymer solution used in the polymerization for obtaining the conjugated diene polymer chain having an active end. Further, in this case, the siloxane compound is preferably dissolved in an inert solvent, and then added to the polymerization system. The solution concentration is preferably in the range of 1 to 50% by weight. The reaction temperature is not particularly limited, but is typically 0 to 120° C. The reaction time is also not particularly limited, but is typically 1 minute to 1 hour.
Although the timing of adding the siloxane compound to the solution containing the conjugated diene polymer chain having an active end is not particularly limited, it is preferable to add the siloxane compound to the solution when the polymerization reaction is not completed and the monomers are also present in the solution containing the conjugated diene polymer chain having an active end, more specifically when the monomers are present in an amount of 100 ppm or more, more preferably 300 to 50,000 ppm in the solution containing the conjugated diene polymer chain having an active end. Such addition of the siloxane compound suppresses secondary reactions between the conjugated diene polymer chain having an active end and impurities and the like in the polymerization system and enables successful control of the reaction.
The modification step is for reacting the siloxane compound as a modifier with the active end of the conjugated diene polymer chain having an active end obtained in the polymerization step. The active end of the conjugated diene polymer chain reacts with the silicon atom in the siloxane structure. Alternatively, a portion of the active end of the conjugated diene polymer chain reacts with an alkoxy group or an epoxy group in a side chain of a polyorganosiloxane represented by General Formula (1) (alkoxy group, epoxy group, or the like forming X2 which is an essential moiety in General Formula (1)). In the modification step, the reaction described above results in introduction of a modifying structure derived from the siloxane into the conjugated diene copolymer chain. Thus, the functional group interactive with silica can be introduced to the conjugated diene polymer.
Specifically, it is presumed that as a result of the reaction of the active end of the conjugated diene polymer chain with the silicon atom in the siloxane structure, the conjugated diene polymer chain forms a new bond between the silicon atom in the siloxane structure and the active end of the conjugated diene polymer chain such that a modifying structure derived from the siloxane is introduced to the active end of the conjugated diene polymer chain, and at the same time, the oxygen atom in the siloxane structure and the metal atom in the active end of the conjugated diene polymer chain form a group represented by —O-M+ (wherein M is an alkali metal atom, an alkaline earth metal atom, or a lanthanide-series metal atom) as a residue of the reaction between them.
Alternatively, it is presumed that when a polyorganosiloxane represented by General Formula (1) is used as the siloxane compound, the active end of the conjugated diene polymer chain reacts with an epoxy group in a side chain of the polyorganosiloxane such that the epoxy ring is opened to form a new bond between the carbon atom at the ring-opened site of the epoxy group and the active end of the conjugated diene polymer chain. As a result, the siloxane structure is introduced to the end of the conjugated diene polymer chain, and at the same time, the oxygen atom in the epoxy group and the metal atom in the active end of the conjugated diene polymer chain form a group represented by —O-M+ as a residue of the reaction between them. Alternatively, the active end of the conjugated diene polymer chain reacts with an alkoxide group in a side chain of the polyorganosiloxane to eliminate the alkoxy group, and the conjugated diene polymer chain forms a new bond between the silicon atom in the siloxane structure and the active end of the conjugated diene polymer chain such that the siloxane structure is introduced to the end of the conjugated diene polymer chain.
In particular, when the amount of the siloxane compound used in the modification step is 1 mol or more based on the number of (—Si—O—) repeating units per mol of the polymerization initiator, a modifying structure derived from the siloxane can be introduced into almost all conjugated diene polymer chains having an active end obtained in the polymerization step. Accordingly, the alkyl metal group as the active end of the conjugated diene polymer chain having an active end obtained in the polymerization step, that is, the —R-M+ group can be almost completely consumed, and in place thereof, a group represented by —O-M+ is formed as a reaction residue.
In the present invention, a compound having a protected primary amino group and an alkoxysilyl group can be used as the modifier having a functional group interactive with silica. Examples thereof include N,N-bis(trimethylsilyl)aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, N,N-bis(trimethylsilyl)aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)amino propyltriethoxysilane, N,N-bis(trimethylsilyl)amino propyl methyldiethoxysilane, N,N-bis(trimethylsilyl)aminoethyltirmethoxysilane, N,N-bis(trimethylsilyl)aminoethyltriethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldiethoxysilane, and the like.
Moreover, in the present invention, a polyfunctional compound having two or more epoxy groups and one or more nitrogen-containing groups in the molecule can be used as the modifier having a functional group interactive with silica. More preferably, a polyfunctional compound represented by General Formula (4) below is used.
In General Formula (4), R10 and R11 are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms and having an ether structure and/or a tertiary amine, R12 and R13 are each hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having an ether and/or a tertiary amine, R1 is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and having at least one group of ether structures, tertiary amines, epoxy, carbonyl, and halogens, and “s” is 1 to 6.
In the present invention, a compound having a silyl group with two or more alkoxy substituent groups and having one or more nitrogen atoms can also be used as the modifier having a functional group interactive with silica. Examples of such compounds include compounds represented by General Formula (5) below, hydrocarbyloxysilanes having a cyclic amino group including two or more nitrogen atoms represented by General Formula (6) below, hydrocarbyloxysilanes having functional groups such as other cyclic amines, non-cyclic amines, imines, and isocyanates, cyclic azasilanes, and the like.
(In General Formula (5), R15 and R16 are each independently an alkyl or aryl group having 1 to 20 carbon atoms, R17 is an alkylene group having 1 to 20 carbon atoms, R18 and R19 are hydrocarbon groups having 1 to 6 carbon atoms, which may be the same or different, and form a 5-membered or larger ring structure with the two adjacent Ns, R20 is a hydrocarbon group having 1 to 20 carbon atoms, and “u” is an integer of 2 or 3.)
(In General Formula (6), R15 to R20 and “u” are as defined above for General Formula (5), and R21 is a hydrocarbon group having 1 to 20 carbon atoms or an organo-substituted silyl group.)
In the present invention, a silane-sulfide compound represented by General Formula (7) below can also be used as the modifier having a functional group interactive with silica:
(R22O)x(R23)ySi—R24—S—SiR25 (7)
(In General Formula (7), Si represents silicon, S represents sulfur, O represents oxygen, “x” is an integer selected from 1, 2, and 3, “y” is an integer selected from 0, 1, and 2, and “x+y” is 3; and R22, R23, and R25 are alkyl groups having 1 to 16 carbon atoms, which may be the same or different from one another, and R24 is an aryl group, an alkylaryl group, or an alkyl group having 1 to 16 carbon atoms.)
In the present invention, a reactive polysiloxane compound represented by General Formula (8) below can be used as the siloxane compound having a functional group interactive with silica:
Y1—CH2CH2—Si(R26)(R27)—{O—Si(R26)(R27)}2—CH2CH2—Y1 (8)
In General Formula (8), Y1 is (X7)a(R28)bSi— where X7 is a halogen and R28 is a lower alkyl group having 20 or less carbon atoms; R26 and R27 are each a lower alkyl group having 20 or less carbon atoms, “a” is 2 or 3, “b” is 0 or 1, “a+b” is 3, and “z” is 1 to 50000.
In the present invention, an amide compound may be used as an end modifier. Examples thereof include N-substituted cyclic amides such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, and N-methyl-ε-caprolactam; N-substituted cyclic ureas such as 1,3-dimethylethyleneurea and 1,3-diethyl-2-imidazolidinone; N-substituted aminoketones such as 4,4′-bis(dimethylamino)benzophenone and 4,4′-bis(diethylamino)benzophenone; aromatic isocyanates such as diphenylmethane diisocyanate and 2,4-tolylene diisocyanate; N, N-disubstituted amino alkyl methacrylamides such as N, N-dimethylaminopropylmethacrylamide; N-substituted aminoaldehydes such as 4-N, N-dimethylaminobenzaldehyde; N-substituted carbodiimides such as dicyclohexylcarbodiimide; Schiff bases such as N-ethylethylideneimine and N-methylbenzylideneimine; pyridyl group-containing vinyl compounds such as 4-vinylpyridine; and the like.
When the modification is performed using a siloxane compound as the modifier having a functional group interactive with silica, it is preferred to further react a compound represented by General Formula (9) below with the conjugated diene polymer chain after the reaction with the siloxane compound.
In General Formula (9), R29 is a hydrocarbyl group, A1 is a group reactive with an alkyl metal group as the active end of the conjugated diene copolymer chain having an active end or the reaction residue which is created by the reaction between the conjugated diene copolymer chain having an active end and the siloxane compound, A2 is a nitrogen atom-containing group, “p” is an integer of 0 to 2, “q” is an integer of 1 to 3, “r” is an integer of 1 to 3, and “p+q+r” is 4.
The compound represented by General Formula (9) is presumed to react with the alkyl metal group as the active end of the conjugated diene polymer chain obtained in the polymerization step, that is, —R-M+, or the group represented by —O-M+ as the reaction residue of the reaction with the siloxane compound (which is intended to include a hydroxyl group created as a result of conversion by hydrolysis of the group represented by —O-M+). When the siloxane compound is used in an amount of 1 mol or more based on the number of (—Si—O—) repeating units per mol of the polymerization initiator to almost completely consume the group represented by —R-M+, the compound represented by General Formula (9) can be almost completely reacted with the group represented by —O-M+ as the reaction residue of the reaction with the siloxane compound. Thus, the modifying structure derived from the compound represented by General Formula (9) can be appropriately introduced via the structure derived from the siloxane compound to the conjugated diene polymer chain. Thereby, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
In the compound represented by General Formula (9), R29 in General Formula (9) is a hydrocarbyl group, such as an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group, and is preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and the like. Among these, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.
In the compound represented by General Formula (9), A1 in General Formula (9) is a group reactive with the alkyl metal group (i.e., R-M+) as the active end of the conjugated diene polymer chain having an active end or the reaction residue created by the reaction between the conjugated diene polymer chain having an active end and the siloxane compound (group typically represented by —O-M+), and is preferably a group represented by —OR30 (where R30 is a hydrogen atom or a hydrocarbyl group). Examples of hydrocarbyl groups which can be R30 include alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, and the like. From the viewpoint of reactivity with the alkyl metal group or the reaction residue, alkyl groups having 1 to 6 carbon atoms are preferred. Examples of alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and the like. Among these, a methyl group and an ethyl group are more preferred.
In the compound represented by General Formula (9), A2 in General Formula (9) is a nitrogen atom-containing group, and is not particularly limited as long as the group has a nitrogen atom. Preferred are organic groups having a nitrogen atom, and examples thereof include a 3-aminopropyl group, a 4-aminobutyl group, a 3-(2-aminoethylamino)propyl group, a 2-dimethylaminoethyl group, a 3-dimethylaminopropyl group, a 3-diethylaminopropyl group, a 3-dipropylaminopropyl group, a 3-dibutylaminopropyl group, a 3-phenylmethylaminopropyl group, a 3-(4-methylpiperazinyl)propyl group, an N, N-bis(trimethylsilyl)aminopropyl group, an N, N-bis(triethylsilyl)aminopropyl group, an N,N′,N′-tris(trimethylsilyl)-N-(2-aminoethyl)-3-aminopropyl group, and the like. Among these, to obtain a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level, groups containing a primary amino group having active hydrogen atoms and/or a secondary amino group having an active hydrogen atom, such as a 3-aminopropyl group, a 4-aminobutyl group, and a 3-(2-aminoethylamino)propyl group, are preferred among these. Note that “active hydrogen atom” means a hydrogen atom bound to an atom other than carbon, and the binding energy thereof is preferably lower than that of the carbon-hydrogen bonds of a polymethylene chain.
In the compound represented by General Formula (9), “p” is an integer of 0 to 2, “q” is an integer of 1 to 3, “r” is an integer of 1 to 3, and “p+q+r” is 4. From the viewpoint of reactivity with the alkyl metal group as the active end of the conjugated diene polymer chain having an active end or the reaction residue created by the reaction of the conjugated diene polymer chain having an active end with the siloxane compound, “p”, “q”, and “r” are preferably an integer of 0 or 1, an integer of 2 or 3 and an integer of 1 or 2, respectively, and “p”, “q”, and “r” are more preferably 0, 3, and 1, respectively. Note that when “p” is 2, the two groups represented by R29 in the molecule of the compound represented by General Formula (9) may be the same or different from each other. Similarly, when “q” is 2 or 3, the multiple groups represented by A1 in the molecule of the compound represented by General Formula (9) may be the same or different from each other, and when “r” is 2 or 3, the multiple groups represented by A2 in the molecule of the compound represented by General Formula (9) may be the same or different from each other.
Specific examples of compounds represented by General Formula (9) include, but are not particularly limited to, the followings: Examples of compounds in which A2 in General Formula (9) is a group containing a primary amino group having active hydrogen atoms and/or a secondary amino group having an active hydrogen atom include compounds having a 3-aminopropyl group as A2, such as 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-aminopropyltriethoxysilane; compounds having a 4-aminobutyl group as A2, such as 4-aminobutyldimethylmethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyldimethylethoxysilane, 4-aminobutylmethyldiethoxysilane, and 4-aminobutyltriethoxysilane; compounds having a 3-(2-aminoethylamino)propyl group as A, such as 3-(2-aminoethylamino)propyldimethylmethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyldimethylethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, and 3-(2-aminoethylamino)propyltriethoxysilane; and the like.
Specific examples of compounds in which A2 in General Formula (9) is a group other than groups containing a primary amino group having active hydrogen atoms and/or a secondary amino group having an active hydrogen atom include compounds having a 3-dimethylaminopropyl group as A2, such as 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-dimethylaminopropyldimethylmethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3-dimethylaminopropylmethyldiethoxysilane, and 3-dimethylaminopropyldimethylethoxysilane; compounds having a 3-diethylaminopropyl group as A2, such as 3-diethylaminopropyltrimethoxysilane, 3-diethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyldimethylmethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-diethylaminopropylmethyldiethoxysilane, and 3-diethylaminopropyldimethylethoxysilane; compounds having a 3-dipropylaminopropyl group as A2, such as 3-dipropylaminopropyltrimethoxysilane, 3-dipropylaminopropylmethyldimethoxysilane, 3-dipropylaminopropyldimethylmethoxysilane, 3-dipropylaminopropyltriethoxysilane, 3-dipropylaminopropylmethyldiethoxysilane, and 3-dipropylaminopropyldimethylethoxysilane; compounds having a 3-dibutylaminopropyl group as A2, such as 3-dibutylaminopropyltrimethoxysilane, 3-dibutylaminopropylmethyldimethoxysilane, 3-dibutylaminopropyldimethylmethoxysilane, 3-dibutylaminopropyltriethoxysilane, 3-dibutylaminopropylmethyldiethoxysilane, and 3-dibutylaminopropyldimethylethoxysilane; compounds having a 3-phenylmethylaminopropyl group as A2, such as 3-phenylmethylaminopropyltrimethoxysilane, 3-phenylmethylaminopropylmethyldimethoxysilane, 3-phenylmethylaminopropyldimethylmethoxysilane, 3-phenylmethylaminopropyltriethoxysilane, 3-phenylmethylaminopropylmethyldiethoxysilane, and 3-phenylmethylaminopropyldimethylethoxysilane; compounds having a 3-(4-methylpiperazinyl)propyl group as A2, such as 3-(4-methylpiperazinyl)propyltrimethoxysilane, 3-(4-methylpiperazinyl)propylmethyldimethoxysilane, 3-(4-methylpiperazinyl)propyldimethylmethoxysilane, 3-(4-methylpiperazinyl)propyltriethoxysilane, 3-(4-methylpiperazinyl)propylmethyldiethoxysilane, and 3-(4-methylpiperazinyl)propyldimethylethoxysilane;
compounds having an N, N-bis(trimethylsilyl)aminopropyl group as A2, such as N, N-bis(trimethylsilyl)aminopropyltrimethoxysilane, N, N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldimethoxysilane, and N, N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane; compounds having an N, N-bis(triethylsilyl)aminopropyl group as A2, such as N, N-bis(triethylsilyl)aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(triethylsilyl)aminopropylmethyldimethoxysilane, and N, N-bis(triethylsilyl)aminopropylmethyldiethoxysilane; compounds having an N,N′,N′-tris(trimethylsilyl)-N-(2-aminoethyl)-3-aminopropyl group as A2, such as N,N′,N′-tris(trimethylsilyl)-N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N,N′,N′-tris(trimethylsilyl)-N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N′,N′-tris(trimethylsilyl)-N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N,N′,N′-tris(trimethylsilyl)-N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane; and the like.
The amount of the compound represented by General Formula (9) used is not particularly limited, but is preferably 0.1 to 5 mol, more preferably 0.2 to 2 mol, still more preferably 0.4 to 1.5 mol per mol of the polymerization initiator used in the polymerization step. When the amount of the compound represented by General Formula (9) falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
The timing of adding the compound represented by General Formula (9) to the solution containing the conjugated diene polymer chain is not particularly limited as long as it is added after addition of the siloxane compound. For example, the compound represented by General Formula (9) can be added to the solution containing the conjugated diene polymer chain when the polymerization reaction is not completed and the monomers are also present in the solution, more specifically when the monomers are present in an amount of 100 ppm or more, more preferably 300 to 50,000 ppm in the solution containing the conjugated diene polymer chain. The addition of the compound represented by General Formula (9) at such a timing suppresses secondary reactions between the conjugated diene polymer chain and impurities and the like in the polymerization system and enables successful control of the reaction. Alternatively, before or after the compound represented by General Formula (9) is added to the solution containing the conjugated diene polymer chain, water or an alcohol such as methanol may be added to the solution to hydrolyze the group represented by —O-M+ created as the reaction residue of the reaction with the siloxane compound into a hydroxyl group, and then the modification reaction may be performed. When the compound represented by General Formula (9) is added to the solution containing the conjugated diene polymer chain, the compound represented by General Formula (9) may be dissolved in an inert solvent before being added, or may be added as it is without being dissolved in an inert solvent. The reaction temperature and the reaction time may be the same as those for the reaction using the siloxane compound.
After the reaction with the compound represented by General Formula (9), a known polymerization terminator or the like is added as needed to deactivate the reaction system, and then an antioxidant such as a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer, a crumb forming agent, a scale inhibitor, and the like are added to the reaction solution as needed. Subsequently, the polymerization solvent is separated from the reaction solution by direct drying, steam stripping, or the like to recover the conjugated diene polymer. The conjugated diene polymer may be recovered as an oil extended rubber by mixing an extender oil with the polymer solution before the separation of the polymerization solvent from the reaction solution.
Examples of oil extenders used to collect the conjugated diene polymer as an oil extended rubber include paraffin-based, aromatic-based, and naphthene-based oil-based softening agents, plant-based softening agents, fatty acids, and the like. When an oil-based softening agent is used, the content of polycyclic aromatic compounds extracted by the method of IP346 (test method of THE INSTITUTE PETROLEUM of the U.K.) is preferably less than 3%. When an oil extender is used, the amount thereof is preferably 1 to 100 parts by weight, more preferably 2 to 60 parts by weight, further preferably 3 to 50 parts by weight relative to 100 parts by weight of the conjugated diene polymer.
Although the above description is mainly based on the examples where a siloxane compound and a compound represented by General Formula (9) are used as the modifier having a functional group interactive with silica, the modifier having a functional group interactive with silica may be any compound which is reactive with the active end of the conjugated diene polymer chain having an active end obtained in the polymerization step and has a functional group interactive with silica, and is not particularly limited.
In order to introduce the functional group interactive with silica to the conjugated diene polymer, a method of introducing the functional group interactive with silica in the polymerization step can be selected instead of or in addition to the method of reacting the modifier having a functional group interactive with silica with the conjugated diene polymer chain having an active end obtained in the polymerization step. Specifically, in the polymerization step, a compound having a functional group reactive with the monomers used in the polymerization step and interactive with silica may also be copolymerized to introduce the functional group interactive with silica. Examples of the functional group interactive with silica include, but are not particularly limited to, nitrogen atom-containing functional groups, silicon atom-containing functional groups, oxygen atom-containing functional groups, and the like. Among these, preferred are silicon atom-containing functional groups because they are more interactive with silica.
Examples of silicon atom-containing modifiers which can be used in the polymerization step include (dimethylamino)dimethylvinylsilane, (ethylmethylamino)dimethylvinylsilane, (diethylamino)dimethylvinylsilane, (ethyl-n-propylamino)dimethylvinylsilane, (ethylisopropylamino)dimethylvinylsilane, (di-n-propylamino)dimethylvinylsilane, (diisopropylamino)dimethylvinylsilane, (n-butyl-n-propylamino)dimethylvinylsilane, (di-n-butylamino)dimethylvinylsilane,
The compound having a functional group interactive with silica used in the polymerization step may be one or more selected from the group consisting of 4,4′-vinylidenebis(n,n-dimethylaniline), 3-(2-pyrolydinoethyl)styrene, 4-(2-pyrolydinoethyl)styrene, and (3-(2-pyrolydino-1-methylethyl)-alpha-methylstyrene.
In the present invention, before the conjugated diene polymer chain having an active end is reacted with the modifier having a functional group interactive with silica, such as a siloxane compound, part of the active ends of the conjugated diene polymer chains having an active end may be coupled or modified by adding a coupling agent or a modifier usually used in the related art in the range not inhibiting the effects of the present invention into the polymerization system.
The coupling ratio of the conjugated diene polymer used in the present invention is not particularly limited, but is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight. When the coupling ratio falls within the above ranges, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained. Note that the coupling ratio refers to the weight fraction of polymer molecules having a molecular weight at least 1.8 times the peak top molecular weight of the conjugated diene polymer chain having an active end before the reactions with the modifier having a functional group interactive with silica, such as the siloxane compound or the compound represented by General Formula (9), and a coupling agent and an additional modifier optionally used, in the total weight of the finally obtained conjugated diene polymer. The molecular weights are measured as polystyrene-equivalent molecular weights determined by gel permeation chromatography.
Examples of the coupling agent optionally used in the present invention include, but are not particularly limited to, halogenated metal compounds. Specifically, examples thereof include silicon tetrachloride, hexachlorodisilane, bis(trichlorosilyl) methane, 1,2-bis(trichlorosilyl)ethane, 1,3-bis(trichlorosilyl)propane, 1,4-bis(trichlorosilyl)butane, 1,5-bis(trichlorosilyl)pentane, and 1,6-bis(trichlorosilyl)hexane. Among these, hexachlorodisilane, 1,2-bis(trichlorosilyl)ethane, or 1,6-bis(trichlorosilyl)hexane can be used. Besides, tin tetrachloride can also be used.
The rubber composition for heavy-load tires according to the present invention comprises silica in addition to the above-mentioned conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica.
Examples of silica which can be used in the present invention include, but are not particularly limited to, dry white carbon, wet white carbon, colloidal silica, precipitated silica, and the like. Alternatively, a carbon-silica dual phase filler comprising silica carried on the surface of carbon black may also be used. Among these, preferred is wet white carbon containing hydrous silicic acid as the main component. These silicas may be used alone or in combination of two or more.
The silica has a nitrogen adsorption specific surface area determined by the BET method of preferably 30 to 500 m/g, more preferably 50 to 400 m2/g, still more preferably 140 to 250 m2/g, particularly preferably 180 to 240 m2/g. When silica having a specific surface area within the above ranges is used, a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained. The silica has a pH of preferably less than 7, more preferably 5 to 6.9. The nitrogen adsorption specific surface area can be measured by the BET method in accordance with ASTM D3037-81.
The amount of the silica present in the rubber composition for heavy-load tires according to the present invention is preferably 10 to 200 parts by weight, more preferably 15 to 100 parts by weight, still more preferably 20 to 50 parts by weight, particularly preferably 22 to 40 parts by weight relative to 100 parts by weight of rubber components in the rubber composition for heavy-load tires. When the amount of the silica present falls within the above ranges, the silica is favorably dispersed during production, and a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained.
Preferably, the rubber composition for heavy-load tires according to the present invention further comprises carbon black in addition to the conjugated diene polymer having a glass transition temperature (Tg) of −50° C. or lower and having a functional group interactive with silica, and silica. When carbon black is further contained, a cross-linked rubber having higher wear resistance can be obtained.
Examples of carbon black include furnace black, acetylene black, thermal black, channel black, graphite, and the like. Among these, preferred is furnace black, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and the like. These may be used alone or in combination.
The carbon black has a nitrogen adsorption specific surface area determined by the BET method of preferably 30 m/g or more, more preferably 30 to 170 m/g, still more preferably 70 to 160 m2/g, particularly preferably 110 to 150 m2/g. When carbon black having a specific surface area within the above ranges is used, a cross-linked rubber having higher wear resistance can be obtained. The nitrogen adsorption specific surface area can be measured by the BET method in accordance with JIS K-6217.
The carbon black has a DBP absorption determined by the A method of preferably 60 to 160 cm3/100 g, more preferably 85 to 150 cm3/100 g, still more preferably 110 to 145 cm3/100 g. When carbon black having a DBP absorption within the above ranges is used, a cross-linked rubber having higher wear resistance can be obtained. The DBP absorption can be measured by the A method in accordance with JIS Z-8091.
The carbon black has an iodine adsorption of preferably 25 to 170 mg/g, more preferably 70 to 160 mg/g, still more preferably 110 to 150 mg/g. When carbon black having an iodine adsorption within the above ranges is used, a cross-linked rubber having higher wear resistance can be obtained. The iodine adsorption can be measured in accordance with JIS Z-8091.
The amount of the carbon black present in the rubber composition for heavy-load tires according to the present invention is preferably 10 to 200 parts by weight, more preferably 15 to 100 parts by weight, still more preferably 20 to 50 parts by weight, particularly preferably 22 to 40 parts by weight relative to 100 parts by weight of the rubber components in the rubber composition for heavy-load tires. When the amount of carbon black present falls within the above ranges, a cross-linked rubber having more appropriately enhanced wear resistance can be obtained.
The rubber composition for heavy-load tires according to the present invention preferably further comprises a natural rubber as a rubber component in addition to the conjugated diene copolymer having a glass transition temperature (Tg) of −50° C. or lower and having a functional group interactive with silica. Examples of usable natural rubbers besides normal natural rubber include modified natural rubbers such as epoxidized natural rubbers obtained by introducing an epoxy group, and hydrogenated natural rubbers. These rubbers may be used in combination. When a natural rubber is contained, a cross-linked rubber having further improved chipping resistance can be obtained.
The amount of the natural rubber present in the rubber composition for heavy-load tires according to the present invention is preferably 10 to 80% by weight, more preferably 30 to 70% by weight, still more preferably 40 to 60% by weight, particularly preferably 45 to 55% by weight in 100 parts by weight of the total rubber component in the rubber composition for heavy-load tires according to the present invention. When the natural rubber is present in an amount within the above ranges, a cross-linked rubber having further improved chipping resistance can be obtained.
Besides the above-mentioned conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica and the natural rubber optionally used, rubber composition for heavy-load tires according to the present invention may further comprise an additional rubber as a rubber component.
Such an additional rubber may be polybutadiene rubber (which may be high cis BR or low cis BR, or may be a polybutadiene rubber containing crystal fibers formed of 1,2-polybutadiene polymer), polyisoprene rubber, emulsion polymerized styrene-butadiene copolymer rubber, solution polymerization styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, ring-opened polymers of cyclic olefins, hydrogenated conjugated diene polymers, and exclude the conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica. These rubbers can be used alone or in combination.
When such an additional rubber is compounded, the content is preferably 10 to 80% by weight, more preferably 20 to 60% by weight, still more preferably 25 to 40% by weight in the total rubber components in the rubber composition for heavy-load tires according to the present invention.
Among these additional rubbers, styrene-butadiene copolymer rubbers are preferred, and terminally modified styrene butadiene copolymers are more preferred because a cross-linked rubber having low heat buildup, wear resistance, and chipping resistance satisfied at a higher level can be obtained. A styrene-butadiene copolymer rubber can be used, for example, in which the styrene unit content is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and the butadiene unit content is preferably 50 to 95% by weight, more preferably 70 to 90% by weight.
To achieve further reduced heat buildup, the rubber composition for heavy-load tires according to the present invention may further comprise a silane coupling agent. The silane coupling agent is not particularly limited, and a variety of silane coupling agents can be used. In the present invention, sulfide-based, mercapto-based, protected mercapto-based (such as those having a carbonylthio group), thiocyanate-based, vinyl-based, amino-based, methacrylate-based, glycidoxy-based, nitro-based, epoxy-based, or chloro-based silane coupling agents can be suitably used. Specific examples of usable silane coupling agents include bis(3-(triethoxysilyl)propyl) disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-(triethoxysilyl)propyl) tetrasulfide, Y-mercaptopropyltriethoxysilane, 3-[ethoxy-bis(3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silyl]-1-propanethiol, 3-octanoylthio-1-propyl-triethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, γ-trimethoxysilylpropylbenzothiazyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-thiocyanate propyltriethoxysilane, vinyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 3-trimethoxysilylpropylmethacrylate monosulfide, γ-glycidoxypropyltriethoxysilane, 3-nitropropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. NXT-Z100, NXT-Z30, NXT-Z45, NXT-Z60, NXT-Z45, and NXT available from Momentive Performance Materials Inc., Si69, Si75, and VP Si363 available from Evonik Industries AG, and the like can also be used. These silane coupling agents may be used alone or in combination of two or more. One or more of these silane coupling agents may be preliminarily formed into an oligomer, and may be used in the oligomer form. The amount of the silane coupling agent used is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight relative to 100 parts by weight of the silica.
The rubber composition for heavy-load tires according to the present invention preferably further comprises a cross-linking agent. Examples of cross-linking agents include sulfur, halogenated sulfur, organic peroxides, quinone dioximes, organic polyvalent amine compounds, alkylphenol resins having a methylol group, and the like. Among these, sulfur is preferably used. The amount of the cross-linking agent used is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, particularly preferably 1 to 4 parts by weight relative to 100 parts by weight of the rubber components in the rubber composition for heavy-load tires.
Furthermore, besides the components above, necessary amounts of compounding agents such as a cross-linking accelerator, a cross-linking activator, an antioxidant, a filler (excluding the silica and carbon black described above), an activating agent, a process oil, a plasticizer, a lubricant, a tackifier, a compatibilizing agent, a surfactant, and the like can be compounded with the rubber composition for heavy-load tires according to the present invention in accordance with ordinary methods.
In the case where sulfur or a sulfur-containing compound is used as a cross-linking agent, use in combination with a cross-linking accelerator and a cross-linking activator is preferred. Examples of cross-linking accelerators include sulfenamide-based cross-linking accelerators; guanidine-based cross-linking accelerators; thiourea-based cross-linking accelerators; thiazole-based cross-linking accelerators; thiuram-based cross-linking accelerators; dithiocarbamic acid-based cross-linking accelerators; xanthic acid-based cross-linking accelerators; and the like. Among these, preferred are those containing sulfenamide-based cross-linking accelerators. These cross-linking accelerators are used alone or in combination of two or more. The amount of the cross-linking accelerator used is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, particularly preferably 1 to 4 parts by weight relative to 100 parts by weight of the rubber components in the rubber composition for heavy-load tires.
Examples of cross-linking activators include higher fatty acids such as stearic acid; zinc oxide; and the like. These cross-linking activators are used alone or in combination of two or more. The amount of the cross-linking activator used is preferably 0.05 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight relative to 100 parts by weight of the rubber components in the rubber composition for heavy-load tires.
Examples of antioxidants include discoloring age resistors having fatigue resistance and ozone resistance, such as N-isopropyl-N′-phenyl-p-phenylenediamine (IPPD), N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N′-phenyl-p-phenylenediamine (7PPD), and N,N′-bis-(1,4-dimethylpentyl)-p-phenylenediamine (77PD), discoloring age resistors having fatigue protection action but not ozone resistance, such as phenyl-x-naphthylamine (PAN), discoloring age resistors having low fatigue resistance without ozone resistance, such as octylated diphenylamine (ODPA), non-discoloring age resistors having fatigue protection action and favorable thermal protection action, such as styrenated phenol (SPH), and the like. These antioxidants are used alone or in combination of two or more. The amount of the antioxidant is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight relative to 100 parts by weight of the rubber components in the rubber composition for heavy-load tires.
Moreover, the rubber composition for heavy-load tires according to the present invention may contain a resin in addition to the rubber components. The use of a resin imparts tackiness to the rubber composition for heavy-load tires, and enhances the dispersibility of the silica in the rubber composition for heavy-load tires. As a result, it is expected that a cross-linked rubber having a greater balance of chipping resistance, low heat buildup, and wear resistance can be obtained. Further, as an effect similar to that of the plasticizer, the processability of the rubber composition for heavy-load tires can also be improved. Examples of resins include a C5 petroleum resin, a C5/C9 petroleum resin, a C9 petroleum resin, a dicyclopentadiene resin, a terpene resin, a terpene phenol resin, an aromatic modified terpene resin, an alkylphenol-acetylene resin, a rosin resin, a rosin ester resin, an indene resin, a C9 resin containing indene, an x-methylstyrene-indene copolymer resin, a coumarone-indene resin, a farnesene-based resin, a polylimonene resin, and the like. These resins may be modified, or may be hydrogenated. These resins may be used alone or in combination of two or more. The amount of the resin blended is preferably 25 parts by weight or less relative to 100 parts by weight of the rubber components in the rubber composition for heavy-load tires.
To obtain the rubber composition for heavy-load tires according to the present invention, the ingredients may be kneaded according to an ordinary method. For example, a target composition can be obtained by kneading the above-mentioned conjugated diene polymer and silica with the ingredients other than thermally unstable ingredients, such as a cross-linking agent and a cross-linking accelerator, among the ingredients optionally used, and mixing the thermally unstable ingredients, such as a cross-linking agent and a cross-linking accelerator, with the kneaded product. The temperature for kneading of the ingredients other than thermally unstable ingredients, the above-mentioned conjugated diene polymer, and silica is preferably 80 to 200° C., more preferably 120 to 180° C. The kneading time is preferably 30 seconds to 30 minutes. Further, the kneaded product and the thermally unstable ingredients are mixed after the kneaded product is cooled to usually 100° C. or lower, preferably 80° C. or lower.
The cross-linked rubber according to the present invention is obtained by cross-linking the above-mentioned rubber composition for heavy-load tires according to the present invention.
The rubber composition for heavy-load tires according to the present invention can be cross-linked by any method without limitation, and selection can be made depending on the size, shape, or the like of the cross-linked rubber. The rubber composition for heavy-load tires according to the present invention may be placed in a mold, and then shaped and cross-linked at the same time by heating, or the rubber composition for heavy-load tires according to the present invention may be preliminarily shaped, and then cross-linked by heating. The cross-linking temperature is typically 100 to 200° C., preferably 130 to 190° C., and the cross-linking time is typically 1 minute to 24 hours, preferably 2 minutes to 12 hours, still more preferably 3 minutes to 6 hours.
Depending on the shape, the size, and the like thereof, the inside of the cross-linked rubber may not be sufficiently cross-linked, even when the surface thereof is cross-linked. For this reason, the cross-linked rubber may be further heated for secondary cross-linking.
As a heating method, a common method used to cross-link rubber such as press heating, steam heating, oven heating, or hot air heating can be appropriately selected.
Since the cross-linked rubber according to the present invention is prepared using the above-mentioned rubber composition for heavy-load tires according to the present invention, the cross-linked rubber has reduced heat buildup and excellent wear resistance and chipping resistance. Owing to these properties, the cross-linked rubber according to the present invention can be used in a variety of tires, in particular heavy-load tires mounted on trucks (including tractors and trailers), buses, construction vehicles (e.g., dump trucks and graders), and the like. The cross-linked rubber according to the present invention can be used for parts of such tires including treads, carcasses, sidewalls, and beads, and is particularly suitably used as a tread. Moreover, the cross-linked rubber is also suitably used as a tread of a retreaded tire obtained by replacing a worn or degraded tread.
Hereinafter, the present invention will be described in more details with reference to Examples, but these Examples should not be construed as limitations to the present invention. Hereinafter, “parts” is on a weight basis unless otherwise specified. The tests and the evaluations were performed as follows.
Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), and coupling ratio were determined based on a polystyrene-equivalent molecular weight chart obtained by gel permeation chromatography (GPC). The specific measurement conditions of the gel permeation chromatography were as follows:
The coupling ratio was determined based on an elution curve obtained by gel permeation chromatography under the conditions shown above, where the area ratio of a peak part with a peak top molecular weight at least 1.8 times the peak top molecular weight of a peak with the smallest molecular weight to the total elution area was regarded as a coupling ratio value.
The vinyl bond content was measured by H-NMR.
Measurement was performed using a Mooney viscometer (available from SHIMADZU Corporation) in accordance with JIS K6300-1 (2013).
Measurement was performed in a helium atmosphere (gas flow rate: 20.0 mL/min) using a differential scanning calorimeter (available from PerkinElmer Inc., trade name “DSC8500”) in accordance with JIS K6240 (2011). The peak top temperature of a differential curve of the resulting DSC curve was determined as the glass transition temperature (Tg).
The heat buildup of a cross-linked rubber was evaluated by measuring the tan & value at 60° C. of a test piece having a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm using ARES-G2 available from TA Instruments at a dynamic strain of 2.5% and 10 Hz. Heat buildup was determined as an index where the measured value of Comparative Example 1 was 100. A greater index indicates lower heat buildup.
The wear resistance of a cross-linked rubber was evaluated by measuring a test piece having an outer diameter of 50 mm, an inner diameter of 15 mm, and a thickness of 10 mm using an FPS wear testing system (available from Ueshima Seisakusho Co., Ltd.) at a load of 10 N and a slip ratio of 158. Wear resistance was determined as an index where the measured value of Comparative Example 1 was 100. A greater index indicates higher wear resistance.
The heat buildup of a cross-linked rubber was determined by measuring elongation at break by a tensile test using a test piece having a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm in accordance with JIS K6301. Chipping resistance was determined as an index where the measured value of Comparative Example 1 was 100. A greater index indicates better chipping resistance.
To a nitrogen-purged container, 218.1 parts of cyclohexane, 7.5 parts of styrene, and 0.3 parts of tetramethylethylenediamine were added, and the inner temperature of the container was controlled to 50° C. Next, 1.64 parts of n-butyllithium was added, and 92.5 parts of isoprene were added over 80 minutes. Subsequently, these were reacted for 15 minutes to yield a solution containing a polymer block (A) having an active end. The weight average molecular weight (Mw) of the polymer block (A) having an active end in the obtained solution was 6,500, the molecular weight distribution (Mw/Mn) was 1.10, the styrene unit content was 7.5% by weight, the isoprene unit content was 92.5% by weight, and the vinyl bond content was 7.0%.
Under a nitrogen atmosphere, 596.5 parts of cyclohexane and 50.0 parts of 1,3-butadiene were charged into an autoclave with a stirrer, then 9.0 parts of the solution containing the polymer block (A) having an active end obtained in Production Example 1 (the amount corresponding to 2.7 parts of the polymer block (A) having an active end used) were added, and polymerization was started at 50° C. After 30 minutes from the start of polymerization, 50.0 parts of 1,3-butadiene was continuously added over 50 minutes, followed by further stirring for 20 minutes. The highest temperature during the polymerization reaction was 75° C. After it was confirmed that the polymerization conversion ratio reached the range of 95% to 100%, 0.015 parts of 1,6-bis(trichlorosilyl) hexane was added, and reacted for 10 minutes. Thereafter, 0.18 parts of polyorganosiloxane represented by Formula (10) shown below in the form of a 40% xylene solution was added, and reacted for 10 minutes. Another 0.18 parts of polyorganosiloxane represented by Formula (10) shown below in the form of a 40% xylene solution was added, and reacted for 20 minutes. Subsequently, 0.18 parts of 3-(2-aminoethylamino)propyltrimethoxysilane in the form of a 50% xylene solution was added, and reacted for 15 minutes. Thereafter, methanol as a polymerization terminator was added in an amount equivalent to two times the moles of n-butyllithium used, affording a polymer solution containing a terminally modified polybutadiene rubber (P1). To this polymer solution, Irganox 1520L (available from BASF SE) and Irganox 1076 (available from BASF SE) as antioxidants were each added in an amount of 0.20 parts relative to 100 parts of the polymer components contained in the polymer solution. Then, the solvent was removed by steam stripping, followed by hot-air drying to yield a terminally modified polybutadiene rubber (P1) as a solid. The terminally modified polybutadiene rubber (P1) thus obtained was measured for weight average molecular weight, coupling ratio, vinyl bond content, Mooney viscosity, and glass transition temperature. The results thereof are shown in Table 1.
The terminally modified polybutadiene rubber (P1) obtained had a functional group interactive with silica at the polymer chain end, the functional group interactive with silica having a modifying structure derived from polyorganosiloxane represented by Formula (10) shown below and 3-(2-aminoethylamino)propyltrimethoxysilane (modifying structure containing an Si—OH structure, an Si—OCH3 structure, and the like) (the same applies to Production Examples 2 to 4 described later).
A terminally modified polybutadiene rubber (P2) was obtained as a solid by the same method as in Production Example 1 except that in the production of the terminally modified polybutadiene rubber (P1) in Production Example 1, 0.019 parts of tetramethylethylenediamine was charged before the start of the polymerization. The terminally modified polybutadiene rubber (P2) obtained was measured in the same manner as in Production Example 1. The results are shown in Table 1.
A terminally modified polybutadiene rubber (P3) was obtained as a solid by the same method as in Production Example 1 except that in the production of the terminally modified polybutadiene rubber (P1) in Production Example 1, 0.038 parts of tetramethylethylenediamine was charged before the start of the polymerization. The terminally modified polybutadiene rubber (P3) obtained was measured in the same manner as in Production Example 1. The results are shown in Table 1.
A terminally modified polybutadiene rubber (P4) was obtained as a solid by the same method as in Production Example 1 except that in the production of the terminally modified polybutadiene rubber (P1) in Production Example 1, 0.058 parts of tetramethylethylenediamine was charged before the start of the polymerization. The terminally modified polybutadiene rubber (P4) obtained was measured in the same manner as in Production Example 1. The results are shown in Table 1.
Under a nitrogen atmosphere, 525 parts of cyclohexane and 56.8 parts of 1,3-butadiene were charged into an autoclave with a stirrer, then, 2.7 parts of n-butyllithium was added, and polymerization was started at 50° C. After 10 minutes from the start of the polymerization, 39.6 parts of 1,3-butadiene was continuously added over 60 minutes. Thereafter, 3.5 parts of 1,3-butadiene was continuously added over 10 minutes, followed by further stirring for 10 minutes. The highest temperature during the polymerization reaction was 75° C. After it was confirmed that the polymerization conversion ratio reached the range of 95% to 100%, 0.008 parts of tin tetrachloride was added, and reacted for 20 minutes. Thereafter, methanol as a polymerization terminator was added in an amount equivalent to two times the moles of n-butyllithium used, affording a polymer solution containing a tin-coupled polybutadiene rubber (P5). To the polymer solution, Irganox 1520L (available from BASF SE) as an antioxidant was added in an amount of 0.25 parts relative to 100 parts of the polymer components contained in the polymer solution. Next, the solvent was removed by steam stripping, followed by hot-air drying to yield a tin-coupled polybutadiene rubber (P5) as a solid.
A terminally modified polybutadiene rubber (P6) was obtained as a solid by the same method as in Production Example 1 except that in the production of the terminally modified polybutadiene rubber (P1) in Production Example 1, 0.067 parts of tetramethylethylenediamine was charged before the start of the polymerization. The terminally modified polybutadiene rubber (P6) obtained was measured in the same manner as in Production Example 1. The results are shown in Table 1.
In a 250-ml Banbury mixer, 50 parts of natural rubber, 20 parts of the terminally modified polybutadiene rubber (P1) obtained in Production Example 1, and 30 parts of a terminally modified styrene butadiene copolymer (available from ZEON Corporation, trade name “Nipol NS612”, styrene unit content: 15% by weight) were masticated for 30 seconds. Next, 25 parts of silica (1) (available from Solvay S. A., trade name “Zeosil 1165MP”, nitrogen adsorption specific surface area determined by the BET method: 165 m/g), 25 parts of carbon black (1) (available from Tokai Carbon Co., Ltd., trade name “SEAST 9H”, nitrogen adsorption specific surface area determined by the BET method: 142 m2/g), and 2.0 parts of a silane coupling agent: bis(3-(triethoxysilyl)propyl) tetrasulfide (available from Evonik Industries AG, trade name “Si69”) were added, and kneaded at a starting temperature of 110° C. for 1.5 minutes. Thereafter, 3 parts of zinc oxide, 2 parts of stearic acid, and 2 parts of an antioxidant: N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine (available from Ouchi Shinko Chemical Industrial Co., Ltd., trade name “NOCRAC 6C”) were added, and further kneaded for 2.5 minutes, and a kneaded product was discharged from the mixer. The temperature of the kneaded product at the end of the kneading was 150° C. The kneaded product was cooled to room temperature, and was kneaded again in the Banbury mixer at a starting temperature of 110° C. for 3 minutes, and then was discharged from the mixer. Subsequently, a mixture of 1.75 parts of sulfur, 1.0 part of a cross-linking accelerator: N-(tert-butyl)-2-benzothiazole sulfenamide (available from Sanshin Chemical Industry Co., Ltd., trade name “Sanceler NS-G”), and 0.53 parts of a cross-linking accelerator: 1,3-diphenylguanidine (available from Ouchi Shinko Chemical Industrial Co., Ltd., trade name “NOCCELER D”) was added to the obtained kneaded product, and kneaded on an open roll mill at 50° C. Then, a sheet-shaped rubber composition was taken out. The rubber composition thus obtained was press cross-linked at 160° C. for 7 minutes to prepare a cross-linked rubber test piece. The test piece was evaluated for low heat buildup, wear resistance, and chipping resistance. The results are shown in Table 2.
A rubber composition was obtained in the same manner as in Example 1 except that 25 parts of silica (2) (available from Evonik Industries AG, trade name “Ultrasil 9100GR”, nitrogen adsorption specific surface area determined by the BET method: 235 m/g) was used instead of 25 parts of silica (1) in Example 1 and 25 parts of carbon black (2) (available from Tokai Carbon Co., Ltd., trade name “SEAST 7HM”, nitrogen adsorption specific surface area determined by the BET method: 126 m/g) was used instead of 25 parts of carbon black (1), and a cross-linked rubber test piece was prepared and evaluated as above. The results are shown in Table 2.
Rubber compositions were obtained in the same manner as in Example 1 except that 20 parts of the terminally modified polybutadiene rubbers (P2) to (P4) obtained in Production Examples 2 to 4 were used instead of 20 parts of the terminally modified polybutadiene rubber (P1) obtained in Production Example 1, and cross-linked rubber test pieces were prepared and evaluated as above. The results are shown in Table 2.
A rubber composition was obtained in the same manner as in Example 1 except that 20 parts of tin-coupled polybutadiene rubber (P5) obtained in Production Example 5 was used instead of 20 parts of the terminally modified polybutadiene rubber (P1) obtained in Production Example 1, and a cross-linked rubber test piece was prepared and evaluated as above. The results are shown in Table 2.
A rubber composition was obtained in the same manner as in Example 1 except that 20 parts of the terminally modified polybutadiene rubber (P6) obtained in Production Example 6 was used instead of 20 parts of the terminally modified polybutadiene rubber (P1) obtained in Production Example, and a cross-linked rubber test piece was prepared and evaluated as above. The results are shown in Table 2.
Tables 1 to 2 show that the cross-linked rubbers obtained using the rubber compositions each comprising silica and a conjugated diene polymer having a glass transition temperature (Tg) of −60° C. or lower and having a functional group interactive with silica had reduced heat buildup and excellent wear resistance and chipping resistance, and can be suitably used in applications to heavy-load tires (Examples 1 to 5).
In contrast, the cross-linked rubbers obtained using a polybutadiene rubber having a glass transition temperature (Tg) of −60° C. or lower but not having a functional group interactive with silica had insufficient heat buildup, wear resistance, and chipping resistance (Comparative Example 1).
Moreover, the cross-linked rubber obtained using a terminally modified polybutadiene rubber having a functional group interactive with silica and having a glass transition temperature (Tg) higher than −60° C. had insufficient wear resistance (Comparative Example 2).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-057274 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/009156 | 3/9/2023 | WO |
