JPWO2019163772A1 - Rubber cross-linked product - Google Patents

Abstract

It is a rubber crosslinked product obtained by cross-linking a rubber composition containing a conjugated diene-based rubber and an inorganic filler, and is interatomic in a state where the rubber cross-linked product is vibrated by a sine wave of 10 Hz. When measuring the loss tangent using a force microscope, the loss tangent value K (m) of the non-interface component forming a portion other than the interface with the inorganic filler and the ratio φ of the non-interface component among the crosslinked rubber components From (m), the loss tangent value K (i) of the interface component forming the interface with the inorganic filler among the crosslinked rubber components, and the ratio φ (i) of the interface component, according to the following formula (A). Provided is a crosslinked rubber product characterized in that the value of the required additivity parameter is 0.36 or less. Additivity parameter = K (m) x φ (m) + K (i) x φ (i) (A) (where φ (m) + φ (i) = 1)

Description

The present invention relates to a rubber crosslinked product obtained by cross-linking a rubber composition containing a conjugated diene rubber and an inorganic filler. More specifically, the present invention relates to a rubber cross-linked product having excellent wet grip property, low heat generation property and abrasion resistance. Regarding things.

In recent years, due to environmental problems and resource problems, tires for automobiles are strongly required to have low heat generation, and further, from the viewpoint of safety, excellent wet grip is required. A tire obtained by using a rubber composition containing silica as a filler in a conjugated diene rubber has lower heat generation property than a tire obtained by using a conventionally used rubber composition containing carbon black. It is possible to make the tire more fuel-efficient because the tire is improved.

As a conjugated diene-based rubber used to provide such a fuel-efficient tire, Patent Document 1 describes a conjugated diene-based rubber having an isoprene block at one end of a conjugated diene-based polymer chain and an active end at the other end. A conjugated diene-based rubber obtained by reacting a specific tin halide compound with a polymer chain is disclosed.

Special Table 2003-531257

However, in view of the recent increase in the required performance for automobile tires, the rubber crosslinked product using the conjugated diene rubber newly developed in the future includes the rubber using the conjugated diene rubber described in Patent Document 1 above. Compared to crosslinked products, those having even lower heat generation, wet grip properties, and abrasion resistance are desired.
The present invention has been made in view of such an actual situation, and an object of the present invention is to provide a rubber crosslinked product having excellent wet grip property, low heat generation property and wear resistance.

In order to achieve the above object, the present inventors have diligently studied a rubber crosslinked product obtained by cross-linking a rubber composition containing a conjugated diene rubber and an inorganic filler, and as a result, a 10 Hz sine wave. Loss tangent value of the non-interface component that forms a portion of the crosslinked rubber component other than the interface with the inorganic filler when the loss tangent is measured using an atomic force microscope in a state of being vibrated by The ratio of K (m) and the non-interface component φ (m), the loss tangent value K (i) of the cross-linked rubber component forming the interface with the inorganic filler, and the ratio of the interface component φ ( The present invention was completed by finding that a rubber crosslinked product having excellent wet grip property, low heat generation property and abrasion resistance can be obtained by controlling the value of the additivity parameter obtained from i) within a specific range. I came to let you.

That is, according to the present invention, it is a rubber crosslinked product obtained by cross-linking a rubber composition containing a conjugated diene-based rubber and an inorganic filler, and the rubber cross-linked product is subjected to vibration due to a sinusoidal wave of 10 Hz. When the loss tangent is measured using an atomic force microscope in the given state, the loss tangent value K (m) of the non-interface component forming a portion other than the interface with the inorganic filler among the crosslinked rubber components. ) And the ratio φ (m) of the non-interface component, the loss tangent value K (i) of the interfacial component forming the interface with the inorganic filler among the crosslinked rubber components, and the ratio φ (i) of the interfacial component. Therefore, a crosslinked rubber product is provided in which the value of the additive parameter obtained according to the following formula (A) is 0.36 or less.
In the present invention, the conjugated diene rubber is preferably a modified conjugated diene rubber having a modifying group.
In the present invention, the conjugated diene rubber is preferably a modified conjugated diene rubber having a modifying group derived from a silicon atom-containing modifier.
In the present invention, the conjugated diene rubber is preferably a modified conjugated diene rubber having a modifying group derived from a siloxane compound or a nitrogen-containing silane compound.
In the present invention, the glass transition temperature (Tg) of the conjugated diene rubber is preferably -40 to -10 ° C.
In the present invention, the vinyl bond content in the conjugated diene monomer unit in the conjugated diene rubber is preferably 0 to 70 mol%.
In the present invention, the content of the inorganic filler is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the rubber component containing the conjugated diene rubber in the rubber composition.
In the present invention, it is preferable that the inorganic filler is silica.

Further, according to the present invention, there is provided a tire including the above-mentioned rubber crosslinked product.

According to the present invention, it is possible to provide a rubber crosslinked product having excellent wet grip, low heat generation and wear resistance, and a tire including the crosslinked product.

The rubber crosslinked product of the present invention is
A rubber crosslinked product obtained by cross-linking a rubber composition containing a conjugated diene-based rubber and an inorganic filler.
When the loss tangent is measured using an atomic force microscope in a state where the rubber crosslinked product is vibrated by a sine wave of 10 Hz, among the crosslinked rubber components, other than the interface with the inorganic filler. The loss tangent value K (m) of the non-interface component forming the portion, the ratio φ (m) of the non-interface component, and the loss tangent value K of the interface component forming the interface with the inorganic filler among the cross-linked rubber components. The value of the additive parameter obtained from (i) and the ratio φ (i) of the interface component according to the following formula (A) is controlled to 0.36 or less.
Additivity parameter = K (m) x φ (m) + K (i) x φ (i) (A)
(However, φ (m) + φ (i) = 1)

<Rubber composition>
First, the rubber composition used in the present invention will be described.
The rubber composition used in the present invention is a conjugated diene-based rubber composition containing a conjugated diene-based rubber and an inorganic filler.

The conjugated diene rubber used in the present invention is not particularly limited as long as it is a polymer containing a conjugated diene monomer unit as a main structural unit, but is a copolymer obtained by polymerizing one kind of conjugated diene compound. Either a copolymer obtained by copolymerizing two or more kinds of conjugated diene compounds, or a copolymer of one kind or two or more kinds of conjugated diene compounds and a monomer copolymerizable with the conjugated diene compound. There may be.

The conjugated diene compound is not particularly limited, and for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-3-ethyl-1,3 -Butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene and the like can be mentioned. Among these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are particularly preferable. In addition, these conjugated diene compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, the conjugated diene-based rubber used in the present invention may be a copolymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The aromatic vinyl compound is not particularly limited, and is, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene. , 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylnaphthalene, dimethylaminomethylstyrene, dimethylaminoethylstyrene and the like. Can be done. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable, and styrene is particularly preferable. In addition. One of these aromatic vinyl compounds may be used alone, or two or more thereof may be used in combination.

As the conjugated diene-based rubber used in the present invention, those containing 50 to 100% by weight of the conjugated diene monomer unit are preferable, those containing 50 to 90% by weight are more preferable, and those containing 50 to 80% by weight are particularly preferable. It is preferable, and the one containing 0 to 50% by weight of the aromatic vinyl monomer unit is preferable, the one containing 10 to 50% by weight is more preferable, and the one containing 20 to 50% by weight is particularly preferable.

Further, the conjugated diene rubber used in the present invention may be obtained by copolymerizing, in addition to the conjugated diene compound, another monomer copolymerizable with the conjugated diene compound other than the aromatic vinyl compound. Good. Other monomers include, for example, α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids or acid anhydrides such as acrylic acid, methacrylic acid and maleic anhydride; methyl methacrylate, acrylic Unsaturated carboxylic acid esters such as ethyl acid, butyl acrylate; unconjugated diene such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadien, dicyclopentadiene, 5-ethylidene-2-norbornene; etc. Can be mentioned. These monomers are preferably contained in a conjugated diene rubber in an amount of 10% by weight or less, more preferably 5% by weight or less, as a monomer unit.

The glass transition temperature (Tg) of the conjugated diene rubber used in the present invention is not particularly limited, but is preferably -40 to -10 ° C, more preferably 35 to -15 ° C, still more preferably -30 to -17 ° C. Is. When the glass transition temperature (Tg) is in the above range, the obtained rubber crosslinked product has an excellent balance between wet grip and low heat generation.

The vinyl bond content in the conjugated diene monomer unit in the conjugated diene rubber used in the present invention is not particularly limited, but is preferably 0 to 80 mol%, more preferably 5 to 70 mol%, still more preferably. It is 8 to 65 mol%, particularly preferably 30 to 55 mol%. When the vinyl bond content is in the above range, the obtained rubber crosslinked product has an excellent balance between wet grip property and low heat generation property.

The weight average molecular weight (Mw) of the conjugated diene rubber used in the present invention is not particularly limited, but is preferably 50,000 to 2,000,000, more preferably 100,000 to 1,800,000, and even more preferably. It is 150,000 to 1,500,000, particularly preferably 300,000 to 1,200,000. The weight average molecular weight of the conjugated diene rubber can be determined as a polystyrene-equivalent value by gel permeation chromatography (hereinafter, also referred to as GPC) measurement. When the weight average molecular weight of the conjugated diene-based rubber is in the above range, the obtained crosslinked rubber product becomes more excellent in wear resistance.

Further, the molecular weight distribution represented by the ratio (Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the conjugated diene-based rubber used in the present invention is preferably 1.0 to 1.5. It is preferably 1.0 to 1.4, and particularly preferably 1.0 to 1.3. When the value of this molecular weight distribution (Mw / Mn) is in the above range, the obtained rubber crosslinked product becomes more excellent in low heat generation.

The conjugated diene-based rubber used in the present invention can be obtained, for example, by polymerizing a monomer containing at least a conjugated diene compound using a polymerization initiator in an inert solvent, such a method. That is, it is preferably polymerized by the solution polymerization method.

Examples of the conjugated diene compound used as the monomer include the same ones exemplified as the conjugated diene compound that can be used for forming the conjugated diene rubber as described above. Further, as the monomer, an aromatic vinyl compound may be used together with the conjugated diene compound. Examples of the aromatic vinyl compound used as the monomer include the same aromatic vinyl compounds exemplified as the above-mentioned aromatic vinyl compounds that can be used to form the conjugated diene rubber. Further, as the monomer, a conjugated diene compound and another monomer copolymerizable with the conjugated diene compound other than the aromatic vinyl compound may be used. As the other monomer copolymerizable with the conjugated diene compound other than the aromatic vinyl compound used as the monomer, the above-mentioned monomer other than the aromatic vinyl compound that can be used to form the conjugated diene rubber is used. Examples of other monomers copolymerizable with the conjugated diene compound include the same ones exemplified.

The inert solvent used for the polymerization is usually used in solution polymerization and is not particularly limited as long as it does not inhibit the polymerization reaction. Specific examples of the inert solvent include chain aliphatic hydrocarbons such as butane, pentane, hexane, heptane and 2-butene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclohexene; benzene, toluene, xylene and the like. Aromatic hydrocarbons; etc. One of these inert solvents may be used alone, or two or more thereof may be used in combination. The amount of the inert solvent used is such that the monomer concentration is, for example, 1 to 50% by weight, preferably 10 to 40% by weight.

The polymerization initiator used for the polymerization is not particularly limited as long as it can polymerize a monomer containing a conjugated diene compound to give a conjugated diene rubber. Specific examples thereof include a polymerization initiator using an organic alkali metal compound, an organic alkaline earth metal compound, a lanthanum series metal compound, or the like as a main catalyst. Examples of the organic alkali metal compound include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stillbenzylene; dilithiomethane, 1,4-dilithiobutane, 1,4. -Organic polyvalent lithium compounds such as -dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-tris (lithiomethyl) benzene; organic sodium compounds such as sodium naphthalene; organic such as potassium naphthalene Potassium compounds; and the like. Examples of the organic alkaline earth metal compound include din-butylmagnesium, din-hexylmagnesium, diethoxycalcium, calcium distearate, dit-butoxystrontium, diethoxybarium, and diisopropoxybarium. , Diethyl mercaptobarium, dit-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, diketylbarium and the like. Examples of the polymerization initiator using a lanthanum-series metal compound as a main catalyst include lantern-series metals such as lanthanum, cerium, placeodim, neodym, samarium, and gadrinium, and lanthanum-series metals composed of carboxylic acids and phosphorus-containing organic acids. Examples thereof include a polymerization initiator composed of an alkylaluminum compound, an organoaluminum hydride compound, an organoaluminum halide compound and the like as a main catalyst and a co-catalyst. Among these polymerization initiators, an organic monolithium compound and an organic multivalent lithium compound are preferably used, an organic monolithium compound is more preferably used, and n-butyllithium is particularly preferably used. The organic alkali metal compound is used as an organic alkali metal amide compound by reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, hexamethyleneimine, and heptamethyleneimine in advance. May be good. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

The amount of the polymerization initiator used may be determined according to the molecular weight of the desired conjugated diene rubber, but is usually 1 to 50 mmol, preferably 1.5 to 20 mmol, more preferably 1.5 to 20 mmol per 1000 g of the monomer. It is in the range of 2 to 15 mmol.

The polymerization temperature is usually in the range of −80 to + 150 ° C., preferably 0 to 100 ° C., and more preferably 30 to 90 ° C. Any mode such as batch type or continuous type can be adopted as the polymerization mode, but when the conjugated diene compound and the aromatic vinyl compound are copolymerized, the conjugated diene monomer unit and the aromatic vinyl monomer can be used. The batch formula is preferable because it is easy to control the randomness of the combination with the unit.

Further, when the conjugated diene rubber is composed of two or more kinds of monomer units, the bonding mode may be various bonding modes such as block shape, taper shape, and random shape, but the bonding mode may be random. It is preferably a binding mode. By making the shape random, the low heat generation of the obtained rubber crosslinked product can be further enhanced.

Further, when polymerizing a monomer containing a conjugated diene compound, a polar compound is added to an inert organic solvent in order to adjust the vinyl bond content in the conjugated diene monomer unit in the obtained conjugated diene rubber. Is preferable. Examples of the polar compound include ether compounds such as dibutyl ether and tetrahydrofuran; tertiary amines such as tetramethylethylenediamine; alkali metal alkoxides; phosphine compounds; and the like. Among these, ether compounds and tertiary amines are preferable, tertiary amines are more preferable, and tetramethylethylenediamine is particularly preferable. One of these polar compounds may be used alone, or two or more thereof may be used in combination. The amount of the polar compound used may be determined according to the desired vinyl bond content, preferably 0.001 to 100 mol, more preferably 0.01 to 10 mol, based on 1 mol of the polymerization initiator. is there. When the amount of the polar compound used is in this range, the vinyl bond content in the conjugated diene monomer unit can be easily adjusted, and problems due to deactivation of the polymerization initiator are unlikely to occur.

As described above, the conjugated diene rubber can be obtained in the inert solvent. Further, since the conjugated diene rubber thus obtained usually has an active terminal, the unreacted active terminal is deactivated by adding a polymerization terminator to the polymerization solution after the completion of the polymerization reaction. However, from the viewpoint of making the effect of the present invention more remarkable, by further reacting various modifiers with such an active terminal, the conjugated diene rubber is modified and conjugated with a modifying group. It is preferable to use a diene rubber.

The denaturing agent is not particularly limited, and an ordinary denaturing agent used as a denaturing agent for a polymer can be used, but the affinity for an inorganic filler such as silica can be appropriately enhanced. A silicon atom-containing modifier is preferable, and a siloxane compound or a nitrogen-containing silane compound is more preferable, from the viewpoint that the obtained crosslinked rubber product can be made more excellent in wet grip property, low heat generation property and abrasion resistance. ..

The siloxane compound may be any one having a siloxane structure (-Si-O-) as a main chain structure, and is not particularly limited, but an organosiloxane having an organic group in the side chain is preferable, and the following general formula (1) is used. The polyorganosiloxane represented is more preferred.

In the above general formula (1), R ^{1 to} R ⁸ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other. .. X ¹ and X ⁴ are composed of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a group having 4 to 12 carbon atoms containing an epoxy group. Any group selected from the group, which may be the same or different from each other. X ² is a group having 4 to 12 carbon atoms containing alkoxy group or an epoxy group, of 1 to 5 carbon atoms, when X ² have multiple, be different even they are identical to each other Good. X ³ is a group containing 2 to 20 repeating units of alkylene glycol, and when there are a plurality of X ³ , they may be the same or different from each other. m is an integer of 0 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.

In the polyorganosiloxane represented by the general formula (1), examples of the alkyl group having 1 to 6 carbon atoms which can constitute R ^{1 to} R ⁸ , X ¹ and X ⁴ in the general formula (1) include, for example. , Methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and the like. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a methylphenyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easiness of producing the polyorganosiloxane itself.

Further, in the polyorganosiloxane represented by the above general formula (1), examples of the alkoxy group having 1 to 5 carbon atoms that can constitute X ¹ , X ² and X ⁴ include a methoxy group, an ethoxy group, and a propoxy group. , Isopropoxy group and butoxy group and the like. Among these, a methoxy group and an ethoxy group are preferable from the viewpoint of easiness of producing the polyorganosiloxane itself.

Further, in the polyorganosiloxane represented by the above general formula (1), as a group having 4 to 12 carbon atoms containing an epoxy group capable of forming X ¹ , X ² and X ⁴ , for example, the following general formula ( The group represented by 2) can be mentioned.
−Z ¹ −Z ² −E (2)
In the above general formula (2), Z ¹ is an alkylene group or an alkylarylene group having 1 to 10 carbon atoms, Z ² is a methylene group, a sulfur atom or an oxygen atom, and E is a carbon having an epoxy group. It is a hydrocarbon group of several 2 to 10.

The group represented by the general formula (2) is preferably a Z ² is an oxygen atom, Z ² is an oxygen atom, and is more preferable E is a glycidyl group, Z ¹ is carbon It is particularly preferable that the alkylene group has a number of 1 to 3, where Z ² is an oxygen atom and E is a glycidyl group.

Further, in the polyorganosiloxane represented by the general formula (1), as X ¹ and X ^4, among the above, having 4 to 12 carbon atoms containing an epoxy group group, or 1 to 6 carbon atoms Alkyl groups are preferred. As the X ^2, among the above, groups of 4 to 12 carbon atoms containing an epoxy group is preferable. Further, it is more preferable that X ¹ and X ⁴ are alkyl groups having 1 to 6 carbon atoms, and X ² is a group having 4 to 12 carbon atoms containing an epoxy group.

上記一般式（３）中、ａは２〜２０の整数であり、Ｘ^５は炭素数２〜１０のアルキレン基またはアルキルアリーレン基であり、Ｒ^９は水素原子またはメチル基であり、Ｘ^６は炭素数１〜１０のアルコキシ基またはアリールオキシ基である。これらの中でも、ａが２〜８の整数であり、Ｘ^５が炭素数３のアルキレン基であり、Ｒ^９が水素原子であり、かつ、Ｘ^６がメトキシ基であるものが好ましい。Further, in the polyorganosiloxane represented by the general formula (1), X ^3, that is, as the group containing repeating units of alkylene glycol having 2 to 20, preferably a group represented by the following general formula (3) ..

In the above general formula (3), a is an integer of 2 to 20, X ⁵ is an alkylene group or an alkyl arylene group having 2 to 10 carbon atoms, R ⁹ is a hydrogen atom or a methyl group, and X ⁶ is. It is an alkoxy group or an aryloxy group having 1 to 10 carbon atoms. Among these, it is preferable that a is an integer of 2 to 8, X ⁵ is an alkylene group having 3 carbon atoms, R ⁹ is a hydrogen atom, and X ⁶ is a methoxy group.

In the polyorganosiloxane represented by the general formula (1), m is an integer of 0 to 200, preferably an integer of 20 to 150, and more preferably an integer of 30 to 120. When m is 200 or less, the polyorganosiloxane itself represented by the general formula (1) can be more easily produced, its viscosity does not become too high, and its handling becomes easier.

Further, in the polyorganosiloxane represented by the general formula (1), n is an integer of 0 to 200, preferably an integer of 0 to 150, and more preferably an integer of 0 to 120. k is an integer from 0 to 200, preferably an integer from 0 to 150, and more preferably an integer from 0 to 130. The total number of m, n and k is 1 or more, preferably 2 to 400, more preferably 20 to 300, and particularly preferably 30 to 250. When the total number of m, n and k is 1 or more, the reaction between the polyorganosiloxane represented by the above general formula (1) and the active terminal of the conjugated diene rubber is likely to proceed, and further, m, n When the total number of and k is 400 or less, the polyorganosiloxane itself represented by the general formula (1) can be easily produced, its viscosity does not become too high, and its handling becomes easy.

The nitrogen-containing silane compound may be any compound containing a nitrogen atom and a silicon atom in one molecule, and is not particularly limited, but for example, the compounds listed below can be used.

（上記一般式（４）中、Ｒ^１０は、炭素数１〜１２のアルキレン基であり、Ｒ^１０が複数あるときは、それらは互いに同一であっても相違していてもよい。Ｒ^１１〜Ｒ^１９は、それぞれ独立して、炭素数１〜６のアルキル基、または炭素数６〜１２のアリール基である。ｂは１〜１０の整数である。）That is, first, as a first specific example of the nitrogen-containing silane compound, a compound represented by the following general formula (4) can be mentioned.

In (the general formula ^{(4), R 10} is an alkylene group having 1 to 12 carbon ^atoms, when there are a plurality ^{of R 10} s, they may be different from be the same as each other ^{.R 11} ~ R ¹⁹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, respectively. B is an integer of 1 to 10 carbon atoms.)

Specific examples of the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms in the compound represented by the general formula (4) include the same compounds as those in the general formula (1). Can be done.

In the compound represented by the general formula (4), examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, and a propylene group. Among these, a propylene group is preferable.

Specific examples of the hydrocarbyloxysilane compound represented by the above general formula (4) include N, N-bis (trimethylsilyl) -3-aminopropyltrimethoxysilane and N, N-bis (trimethylsilyl) -3-aminopropyl. Examples thereof include triethoxysilane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, and N, N-bis (trimethylsilyl) aminoethyltriethoxysilane.

Further, as a second specific example of the nitrogen-containing silane compound, a compound represented by the following general formula (5) can be mentioned.

In the above general formula (5), R ²⁰ and R ²¹ are independently organic groups having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms. , Or an aryl group having 6 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and further preferably a methyl group, an ethyl group or a benzyl group. .. Further, X ⁷ represents a functional group selected from a hydrocarbyloxy group, a halogen group and a hydroxyl group, and the hydrocarbyloxy group which can be a functional group represented by X ⁷ is not particularly limited, but is limited to a methoxy group, an ethoxy group and n. -Alkoxy groups such as propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; alkenyloxy group such as vinyloxy group and allyloxy group; allyloxy group such as phenoxy group and naphthoxy group An aralkyloxy group such as a benzyloxy group; and the like. Among these, an alkoxy group or an aryloxy group is preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable. The halogen group that can be X ⁷ is not particularly limited, and examples thereof include a fluoro group, a chloro group, a bromo group, and an iodine group, and among these, a chloro group is preferable. Further, X ⁷ may be a hydroxyl group, and the hydroxyl group may be a hydroxyl group obtained by hydrolyzing what was a hydrocarbyloxy group or a halogen group. R ²² is an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group. c is an integer of 0 to 2, d is an integer of 1 to 10, and is preferably an integer of 1 to 6. When X ⁷ or ^{R 22} there is a plurality, a plurality of ^{X 7} or ^{R 22} may be different from be the same as each other.

Specific examples of the compound represented by the general formula (5) include 3- (N, N-dimethylamino) propyltriethoxysilane, 3- (N, N-diethylamino) propyltrimethoxysilane, and 3- (N). , N-diethylamino) propyltriethoxysilane, 3- (N, N-diethylamino) propyltrimethoxysilane, 3- (N, N-dimethylamino) propyldiethoxymethylsilane, 3- (N-benzyl-N-methyl) Amino) propyltrimethoxysilane, 3- (N-phenyl-N-propylamino) pentyltrimethoxysilane, 3- (N, N-dimethylamino) propyltriethoxysilane, 3- (N, N-dimethylamino) propyl Trimethoxysilane, 3- (N-allyl-N-methylamino) propyltrimethoxysilane, 3- (N, N-dimethylamino) propyldimethylethoxysilane, 3- (N, N-dimethylamino) propyltriethoxysilane , 3- (N, N-dimethylamino) propyltrimethoxysilane, 3- (N, N-dimethylamino) propyldiisopropylethoxysilane, 3- (N-methyl-N-phenylamino) propyltrimethoxysilane, 3- Examples thereof include (N, N-bis [trimethylsilyl] amino) propyltrimethoxysilane and 3- (N, N-diethylamino) propyltrichlorosilane.

Further, as a third specific example of the nitrogen-containing silane compound, a compound represented by the following general formula (6) can be mentioned.

In the above general formula (6), R ²³ is an organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and more preferably carbon. It is an alkyl group having a number of 1 to 10 or an aryl group having 6 to 12 carbon atoms. Further, X ⁸ represents a functional group selected from a hydrocarbyloxy group, a halogen group and a hydroxyl group, and specific examples thereof can be the same as X ⁷ of the above general formula (5). R ²⁴ is an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group. e is an integer from 0 to 1. When the X ⁸ there is a plurality, a plurality of X ⁸ may be different from be the same as each other.

Specific examples of the compound represented by the above general formula (6) include 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane and 2,2-diethoxy-1-phenyl-1-aza. -2-Silacyclopentane, 2,2-dipropoxy-1-phenyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-butyl-1-aza-2-silacyclopentane, 2,2 −Diethoxy-1-butyl-1-aza-2-silacyclopentane, 2,2-dipropoxy-1-butyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-trimethylsilyl-1-aza -2-Silacyclopentane, 2,2-dichloro-1-phenyl-1-aza-2-silacyclopentane and the like can be mentioned.

Further, as a fourth specific example of the nitrogen-containing silane compound, a compound represented by the following general formula (7) can be mentioned.

In the above general formula (7), X ⁹ represents a functional group selected from a hydrocarbyloxy group, a halogen group and a hydroxyl group, R ²⁵ represents a hydrocarbon group which may have a substituent, and R ²⁶ and R. ²⁷ are each independently have a substituent a hydrocarbon group having carbon atoms which may 1 to 20, R ²⁶ and R ^27, taken together, form a ring structure together with the nitrogen atom to which they are attached In the case of forming the ring structure, the ring structure may be formed together with a heteroatom other than the nitrogen atom to which they are bonded in addition to the nitrogen atom to which they are bonded. f is an integer of 1-2.

In the general formula (7), X ⁹ represents a functional group selected from a hydrocarbyloxy group, a halogen group and a hydroxyl group, and a specific example thereof can be the same as that of X ^{7 in the} general formula (5). ..

Further, in the above general formula (7), f (that is, the number of functional groups represented by X ⁹ in the formula (7)) is an integer of 1 to 2, and is preferably 2. When f in the general formula (7) is 2, the groups represented by X ⁹ contained in one molecule of the compound represented by the general formula (7) may be the same. , May be different from each other.

In the above general formula (7), R ²⁵ represents a hydrocarbon group which may have a substituent, and the hydrocarbon group which can be R ²⁵ is not particularly limited, but is a methyl group, an ethyl group, or n−. Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group; alkenyl group such as vinyl group and allyl group; alkynyl group such as ethynyl group and propynyl group; phenyl group , Aryl groups such as naphthyl groups; aralkyl groups such as benzyl groups; and the like. Among these, an alkyl group or an aryl group is preferable, and an alkyl group is more preferable. Further, the hydrocarbon group represented by R ²⁵ may have a substituent other than the hydrocarbon group, and the substituent is not particularly limited, but is a carboxyl group, an acid anhydride group, or a hydrocarbylcarbonyl group. , Carbonyl group-containing groups such as alkoxycarbonyl group and acyloxy group, epoxy group, oxy group, cyano group, amino group, halogen group and the like can be mentioned.

In the above general formula (7), R ²⁶ and R ²⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ²⁶ and R ²⁷ are bonded to each other. , A ring structure may be formed together with a nitrogen atom represented by "N" in the general formula (7). When R ²⁶ and ^{R 27} are not bonded to each ^other, as the hydrocarbon group which may be ^{R 26} and ^{R 27,} but are not limited to, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group Alkyl groups such as isobutyl group, sec-butyl group and tert-butyl group; alkenyl groups such as vinyl group and allyl group; alkynyl groups such as ethynyl group and propynyl group; aryl groups such as phenyl group and naphthyl group; benzyl group Aralkill groups such as; etc. Among these, an alkyl group or an aryl group is preferable, an alkyl group is more preferable, and a methyl group or an ethyl group is particularly preferable. When R ²⁶ and R ²⁷ are bonded to each other to form a ring structure, the divalent hydrocarbon group to which R ²⁶ and R ²⁷ are bonded is not particularly limited, but is an n-butylene group (n-butylene group). Forming a 1-pyrrolidine group with a nitrogen atom represented by "N" in the general formula (7)), an n-pentylene group (when forming a 1-piperidine group), a butadienylene group (forming a 1-pyrrol group). If you do), etc.

Further, the hydrocarbon group represented by R ²⁶ and R ²⁷ may have a substituent other than the hydrocarbon group regardless of the presence or absence of ring structure formation, and the substituent is not particularly limited. , Carboxyl group, acid anhydride group, hydrocarbylcarbonyl group, alkoxycarbonyl group, acyloxy group and other carbonyl group-containing groups, epoxy group, oxy group, cyano group, amino group, halogen group and the like can be mentioned. Further, when R ²⁶ and R ²⁷ are bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, the carbon atom and the atom forming the ring structure are "N" in the general formula (7). Heteroatoms other than the nitrogen atom represented by "" may be contained, and examples of such heteroatoms include nitrogen atoms and oxygen atoms.

In the present invention, among the compounds represented by the general formula (7), the hydrocarbon groups represented by R ²⁶ and R ²⁷ are bonded to each other as particularly preferable, and the compound represented by the general formula (7) is ". Examples thereof include those forming a piperazine ring structure together with the nitrogen atom represented by "N". More specifically, it is preferable to use a compound represented by the following general formula (8).

In the general formula (8), X ⁹ , R ²⁵ , and f all represent the same as those in the general formula (7), and R ²⁸ represents a hydrocarbon group having 1 to 20 carbon atoms.

In the above general formula (8), R ²⁸ represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group that can be R ²⁸ is not particularly limited, but is a methyl group, an ethyl group, an n-propyl group, or an isopropyl. Alkyl groups such as groups, n-butyl groups, isobutyl groups, sec-butyl groups and tert-butyl groups; alkenyl groups such as vinyl groups and allyl groups; alkynyl groups such as ethynyl groups and propynyl groups; phenyl groups, naphthyl groups and the like An aryl group of the above; an aralkyl group such as a benzyl group; and the like. Among these, an alkyl group or an aryl group is preferable, an alkyl group is more preferable, and a methyl group is particularly preferable.

Specific examples of the compound represented by the above general formula (7) include 2,2-dimethoxy-8- (4-methylpiperazinyl) methyl-1,6-dioxa-2-silacyclooctane, 2,2. -Diethoxy-8- (4-methylpiperazinyl) methyl-1,6-dioxa-2-silacyclooctane, 2,2-dimethoxy-8- (N, N-diethylamino) methyl-1,6-dioxa- 2-Silacyclooctane, 2-methoxy-2-methyl-8- (4-methylpiperazinyl) methyl-1,6-dioxa-2-silacyclooctane, 2,2-dichloro-8- (4-methyl) Piperazinyl) Methyl-1,6-dioxa-2-silacyclooctane and the like.

Further, as a fifth specific example of the nitrogen-containing silane compound, a compound represented by the following general formula (9) can be mentioned.

In the general formula (9), X ¹⁰ represents a functional group selected from a hydrocarbyloxy group, a halogen group and a hydroxyl group, and specific examples thereof can be the same as X ^{7 in the} general formula (5). .. R ²⁹ is an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group. Further, R ³⁰ , R ³¹ , and R ³² are independently organic groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably methyl groups or ethyl groups. is there. g is an integer of 0 to 2, h is an integer of 1 to 10, and j is an integer of 1 to 10. When X ¹⁰ or ^{R 29} is plural, plural ^{X 10} or ^{R 29} may be different from be the same as each other.

Specific examples of the compound represented by the above general formula (9) include 3- [N-2- {N', N'-bis (trimethylsilyl) amino} ethyl-N-trimethylsilylamino] propyltriethoxysilane, 3 -[N-2- {N', N'-bis (triethylsilyl) amino} ethyl-N-triethylsilylamino] propyltriethoxysilane, 3- [N-2- {N', N'-bis (triethyl) Cyril) amino} ethyl-N-triethylsilylamino] propyltrichlorosilane and the like can be mentioned.

Further, as a sixth specific example of the nitrogen-containing silane compound, a compound represented by the following general formula (10) can be mentioned.

In the general formula (10), X ¹¹ represents a functional group selected from a hydrocarbyloxy group, a halogen group and a hydroxyl group, and specific examples thereof can be the same as X ^{7 in the} general formula (5). .. R ³³ is an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group. Further, R ³⁴ and R ³⁵ are independently hydrogen atoms or organic groups having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or carbon. It is an aryl group of the number 6-18. p is an integer of 0 to 2, and q is an integer of 1 to 10. When X ¹¹ or ^{R 33} there is a plurality, a plurality of ^{X 11} or ^{R 33} may be different from be the same as each other.

Specific examples of the compound represented by the above general formula (10) include N- (3-triethoxysilylpropyl) -4-methylpentane-2-imine and N- (3-trimethoxysilylpropyl) -4-. Methylpentane-2-imine, N- (3-triethoxysilylpropyl) propan-2-imine, N- (3-triethoxysilylpropyl) pentane-3-imine, N- (3-trichlorosilylpropyl) -4 -Methylpentane-2-imine and the like.

Among the nitrogen-containing silane compounds, the compound represented by the general formula (5), the general formula (7) or the general formula (9) is preferable, and the general formula (5) or the general formula (7) The compound represented by the above general formula (7) is more preferable, and the compound represented by the above general formula (7) is particularly preferable.

The amount of the modifier used when reacting the above-mentioned modifier with the active end of the conjugated diene rubber is not particularly limited, but the amount of the modifier with respect to 1 mol of the active end of the conjugated diene rubber having the active end. (When an organic alkali metal compound is used as the polymerization initiator, the amount of the modifier per 1 mol of the metal atom in the organic alkali metal compound) is preferably 0.01 to 10.0 mol, preferably 0. It is more preferably 0.02 to 5.0 mol, and particularly preferably 0.05 to 2.0 mol. The denaturing agent may be used alone or in combination of two or more.

The method for reacting the denaturing agent with the active terminal of the conjugated diene rubber is not particularly limited, but the conjugated diene rubber having the active terminal and the denaturing agent are mixed in a solvent capable of dissolving them. Examples include a method of mixing. As the solvent used at this time, those exemplified as the solvent used for the polymerization of the above-mentioned conjugated diene rubber can be used. Further, in this case, it is convenient and preferable to leave the conjugated diene rubber having the active terminal obtained above in the state of the polymerization solution used for the polymerization and add a denaturing agent thereto. At this time, the modifier may be dissolved in the above-mentioned inert solvent used for the polymerization and added into the polymerization system, and the solution concentration thereof is preferably in the range of 1 to 50% by weight. The reaction temperature is not particularly limited, but is usually 0 to 120 ° C., and the reaction time is not particularly limited, but is usually 1 minute to 1 hour.

The timing of adding the modifier to the solution containing the conjugated diene rubber having an active end is not particularly limited, but the polymerization reaction is not completed and a single amount of the solution containing the conjugated diene rubber having an active end is used. A state in which the body is also contained, more specifically, a state in which the solution containing the conjugated diene rubber having an active terminal contains 100 ppm or more, more preferably 300 to 50,000 ppm of a monomer. Therefore, it is desirable to add a modifier to this solution. By adding the modifier in this way, it is possible to suppress side reactions between the conjugated diene rubber having an active terminal and impurities and the like contained in the polymerization system, and to control the reaction satisfactorily.

Before reacting the modifying agent with the conjugated diene rubber having an active end, a part of the active end of the conjugated diene rubber is conventionally used as long as the effect of the present invention is not impaired. A ring agent or the like may be added into the polymerization system to inactivate it.

If the unreacted active terminal remains after the modifier is reacted with the conjugated diene rubber having the active end, a polymerization inhibitor such as alcohol such as methanol, ethanol, isopropanol or water is added to the polymerization solution. It is preferably added to inactivate unreacted active terminals.

If desired, a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer may be added to the solution of the conjugated diene-based rubber (including the case where it is a modified conjugated diene-based rubber; the same applies hereinafter) obtained as described above. Anti-aging agents such as may be added. The amount of the anti-aging agent added may be appropriately determined according to the type and the like. Further, if desired, a spreading oil may be blended to obtain an oil spreading rubber. Examples of the spreading oil include paraffin-based, aromatic and naphthenic petroleum-based softeners, plant-based softeners, fatty acids and the like. When a petroleum-based softener is used, the content of polycyclic aromatics extracted by the method of IP346 (inspection method of THE INSTITUTE PETROLEUM in the United Kingdom) is preferably less than 3%. When the spreading oil is used, the amount used is usually 5 to 100 parts by weight with respect to 100 parts by weight of the conjugated diene rubber.

The conjugated diene rubber thus obtained can be obtained as a solid conjugated diene rubber by separating it from the reaction mixture by removing the solvent by, for example, steam stripping.

The rubber composition used in the present invention contains an inorganic filler in addition to the above-mentioned conjugated diene-based rubber.

The inorganic filler is not particularly limited, but at least one inorganic filler selected from silica and carbon black is preferable, and the obtained rubber crosslinked product can be excellent in low heat generation. , Silica is more preferred.

Examples of silica include dry white carbon, wet white carbon, colloidal silica, and precipitated silica. Among these, wet white carbon containing hydrous silicic acid as a main component is preferable. Further, a carbon-silica dual phase filler in which silica is supported on a carbon black surface may be used. These silicas can be used alone or in combination of two or more. Is (measured by the BET method according to ASTM D3037-81) nitrogen adsorption specific surface area of silica used is preferably 50 to 300 m ² / g, more preferably 80~220m ² / g, particularly preferably 100~170m ² / g. The pH of silica is preferably 5 to 10.

Examples of carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. When carbon black is used, it is preferable to use furnace black, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, T-HS, Examples include T-NS, MAF, and FEF. These carbon blacks can be used alone or in combination of two or more.

The blending amount of the inorganic filler in the rubber composition used in the present invention is preferably 10 to 200 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the rubber component containing the conjugated diene rubber in the rubber composition. It is 30 to 150 parts by weight, more preferably 40 to 100 parts by weight. By setting the blending amount of the inorganic filler in the above range, the processability of the rubber composition becomes excellent, and the obtained crosslinked rubber product can be made excellent in wet grip property and low heat generation property.

When silica is used as the inorganic filler in the rubber composition used in the present invention, a silane coupling agent may be further blended from the viewpoint of further improving low heat generation. Examples of the silane coupling agent include vinyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and 3-octanoylthio-. 1-propyl-triethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) prol) tetrasulfide, γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide, and γ − Trimethoxysilylpropylbenzothiaziltetrasulfide and the like can be mentioned. These silane coupling agents can be used alone or in combination of two or more. The blending amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of silica.

Further, the rubber composition used in the present invention preferably further contains a cross-linking agent. Examples of the cross-linking agent include sulfur-containing compounds such as sulfur and sulfur halide, organic peroxides, quinonedioximes, organic polyvalent amine compounds, and alkylphenol resins having a methylol group. Of these, sulfur is preferably used. The amount of the cross-linking agent to be blended is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, particularly preferably 0.1 part by weight, based on 100 parts by weight of the rubber component containing the conjugated diene rubber in the rubber composition. Is 1 to 4 parts by weight.

Further, in addition to the above components, the rubber composition used in the present invention contains a cross-linking accelerator, a cross-linking activator, an antiaging agent, an organic filler, an activator, a process oil, a plasticizer, a lubricant, and an adhesive according to a conventional method. A required amount of a compounding agent such as an imparting agent can be blended.

When sulfur or a sulfur-containing compound is used as the cross-linking agent, it is preferable to use a cross-linking accelerator and a cross-linking activator in combination. Examples of the cross-linking accelerator include sulfenamide-based cross-linking accelerator; guanidine-based cross-linking accelerator; thiourea-based cross-linking accelerator; thiazole-based cross-linking accelerator; thiuram-based cross-linking accelerator; dithiocarbamic acid-based cross-linking accelerator; xanthate-based Crosslink accelerators; and the like. Among these, those containing a sulfenamide-based cross-linking accelerator are preferable. These cross-linking accelerators may be used alone or in combination of two or more. The blending amount of the cross-linking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, particularly, with respect to 100 parts by weight of the rubber component containing the conjugated diene rubber in the rubber composition. It is preferably 1 to 4 parts by weight.

Examples of the cross-linking activator include higher fatty acids such as stearic acid; zinc oxide; and the like. These cross-linking activators may be used alone or in combination of two or more. The amount of the cross-linking activator to be blended is preferably 0.05 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the rubber component containing the conjugated diene rubber in the rubber composition. is there.

Further, in the rubber composition used in the present invention, a plurality of types of rubber may be used in combination as the conjugated diene rubber. For example, when a conjugated diene rubber containing at least a modified conjugated diene rubber having a modifying group obtained by the above-mentioned production method is used, two or more kinds of rubbers are used as the modified conjugated diene rubber having a modifying group. (For example, rubbers having different modifying groups) may be used in combination, or one or more modified conjugated diene rubbers may be used in combination with other unmodified conjugated diene rubbers. Good. Examples of such other unmodified conjugated diene rubbers include natural rubber, polyisoprene rubber, emulsified polymerized styrene-butadiene copolymer rubber, solution polymerized styrene-butadiene copolymer rubber, and polybutadiene rubber (high cis-BR, It may be a low cis BR, or it may be a polybutadiene rubber containing crystal fibers composed of a 1,2-polybutadiene polymer), a styrene-isoprene copolymer rubber, a butadiene-isoprene copolymer rubber, and a styrene-. Examples thereof include isoprene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, and acrylonitrile-styrene-butadiene copolymer rubber. Among these, natural rubber, polyisoprene rubber, polybutadiene rubber, and solution-polymerized styrene-butadiene copolymer rubber are preferable. These rubbers can be used alone or in combination of two or more. Further, the rubber composition used in the present invention may contain a rubber other than the conjugated diene rubber.

When a rubber containing at least a modified conjugated diene rubber having a modifying group obtained by the above-mentioned production method is used, the content ratio of the modified conjugated diene rubber is 10 of the rubber component in the rubber composition used in the present invention. It preferably occupies ~ 100% by weight, and particularly preferably 50-100% by weight. By including the modified conjugated diene rubber in the rubber component at such a ratio, a rubber crosslinked product having excellent low heat generation and wet grip properties can be obtained.

As a method for obtaining the rubber composition used in the present invention, a method of kneading each component according to a conventional method may be adopted. For example, an inorganic filler excluding heat-unstable components such as a cross-linking agent and a cross-linking accelerator. After kneading the above-mentioned compounding agent and the rubber component containing the conjugated diene rubber described above, a heat-unstable component such as a cross-linking agent or a cross-linking accelerator can be mixed with the kneaded product to obtain the desired composition. it can. The kneading temperature of the compounding agent excluding the heat-unstable component and the rubber component is preferably 80 to 200 ° C., more preferably 120 to 180 ° C., and the kneading time is preferably 30 seconds to 30 minutes. .. Further, the kneaded product and the heat-unstable component are usually mixed after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.

<Rubber crosslinked product>
The rubber crosslinked product of the present invention is obtained by cross-linking a rubber composition containing the above-mentioned conjugated diene rubber and an inorganic filler.
When the loss tangent is measured using an atomic force microscope in a state where the rubber crosslinked product is vibrated by a sine wave of 10 Hz, among the crosslinked rubber components, other than the interface with the inorganic filler. The loss tangent value K (m) of the non-interface component forming the portion, the ratio φ (m) of the non-interface component, and the loss tangent value K of the interface component forming the interface with the inorganic filler among the cross-linked rubber components. The value of the additive parameter obtained from (i) and the ratio φ (i) of the interface component according to the following formula (A) is controlled to 0.36 or less.
Additivity parameter = K (m) x φ (m) + K (i) x φ (i) (A)
(However, φ (m) + φ (i) = 1)

According to the present invention, the rubber crosslinked product is formed by cross-linking a rubber composition containing a conjugated diene-based rubber and an inorganic filler, and is not subjected to vibration by a 10 Hz sinusoidal wave. From the loss tangent value K (m) of the interface component and the ratio φ (m) of the non-interfacial component, and the loss tangent value K (i) of the interface component and the ratio φ (i) of the interface component, the above formula (A) By setting the value of the adaptability parameter obtained according to the above to 0.36 or less, the rubber crosslinked product can be made excellent in wet grip property, low heat generation property and abrasion resistance. In particular, in order to improve wet grip, low heat generation and abrasion resistance, the present inventors have described the interface state between the crosslinked rubber and the inorganic filler in the crosslinked rubber and its presence in the crosslinked rubber. As a result of diligent studies focusing on the ratio, the loss tangential value K (m) of the non-interfacial component and the loss tangent value K (i) of the interfacial component under the state of being vibrated by a 10 Hz sine wave were obtained. By setting the additive parameter AP obtained from the ratio φ (m) of the non-interfacial component and the ratio φ (i) of the interfacial component in the crosslinked rubber component within the above range, the wet grip property of the rubber crosslinked product can be improved. It has been found that low heat generation and wear resistance can be improved. The additive parameter AP in the present invention is obtained by measurement in a micro range of about 1 μm × 1 μm, and as a result of diligent studies by the present inventors, it is found in such a micro range. It was found that the wet grip property, low heat generation property and wear resistance, which are the macro properties of the rubber crosslinked product, can be improved by controlling the additive parameter AP to a specific range based on the measurement result. Is.

The loss tangent value K (m) of the non-interfacial component is the crosslinked rubber portion (inorganic of the crosslinked rubber components) that is substantially unaffected by the inorganic filler among the crosslinked rubber components constituting the rubber crosslinked product. It is the loss tangent value in the portion sufficiently separated from the filler, that is, the non-interfacially formed crosslinked rubber component portion, and the larger the loss tangent value K (m), the more 10 Hz when vibration due to a 10 Hz sine wave is applied. It can be judged that it is easy to move by following a sine wave with a relatively low frequency. Further, the loss tangent value K (i) of the interface component is the loss tangent value in the crosslinked rubber component portion forming the interface with the inorganic filler, that is, the interface-formed crosslinked rubber component portion among the crosslinked rubber components constituting the rubber crosslinked product. It is a value, and the smaller the loss tangent value K (i) is, the more difficult it is to move when vibration is applied by a sine wave of 10 Hz. Therefore, it can be determined that the interaction is strong with the inorganic filler.

Then, in the present invention, the product K (m) × φ (m) of the loss tangent value K (m) of such a non-interface component and its ratio φ (m), and the loss of such an interface component. Additivity parameter AP obtained by adding the product K (i) × φ (i) of the tangent value K (i) and its ratio φ (i) (additivity parameter AP = K (m) × φ (m) + K (i) × φ (i)) is controlled to 0.36 or less, which can improve the wet grip property, low heat generation property and wear resistance of the rubber crosslinked product. is there. The additivity parameter AP is preferably 0.35 or less, more preferably 0.30 or less, still more preferably 0.25 or less. The lower limit thereof is not particularly limited, but is usually 0.1 or more. Here, when measuring the loss tangent value K (m) of the non-interface component and the loss tangent value K (i) of the interface component, the portion corresponding to the non-interface component and the interface component in the cross-linked rubber component. The tangent value of the loss is measured after identifying the part corresponding to, but the ratio φ (m) of the non-interface component is the ratio of the part corresponding to the non-interface component, and the non-interface component. The ratio φ (i) indicates the ratio of the portion corresponding to the interface component, and in the present invention, when the total of these is 1, that is, the ratio φ (m) + the ratio φ (i). It is expressed as a ratio when = 1.

The loss tangent value K (m) of the non-interfacial component and its ratio φ (m) and the loss tangent value K (i) of the interface component and its ratio φ (i) when vibration by a sine wave of 10 Hz is applied. The method for measuring the above is not particularly limited, and the rubber crosslinked product is preferably vibrated at room temperature (25 ° C.) while being vibrated by a 10 Hz sine wave (preferably an amplitude of 1 to 10 nm). Any method may be used as long as the loss tangent (loss tangent = loss elasticity / storage elasticity) can be measured with a resolution of 1 to 300 nm, more preferably 0.1 to 100 nm, but usually, it is interatomic. A force microscope is used. The atomic force microscope is not particularly limited, and an atomic force microscope manufactured by Bruker, an atomic force microscope manufactured by OXFORD INSTRUMENTS, and the like can be used without limitation. Further, in the present invention, the loss tangent is measured by using an atomic force microscope, but it is possible to measure with the above resolution while applying vibration by a 10 Hz sine wave other than the method using an atomic force microscope. If it is a method, it can be used without particular limitation. Further, in the present invention, the loss tangent is measured by applying vibration by a sine wave of 10 Hz, but the frequency of the sine wave is changed by changing the measurement temperature (for example, by setting the temperature other than 25 ° C.). It is also possible. Specifically, it is also possible to change the measurement temperature and the frequency of the sine wave so that the conditions are the same as when vibration by a sine wave of 10 Hz is applied at 25 ° C.

As a specific method for measuring the loss tangent value K (m) of the non-interface component and the loss tangent value K (i) of the interface component when vibration is applied by a 10 Hz sine wave, for example, "Nanorheological" Mapping of Rubbers by Atomic Force microscopy ”, macromolecules, 46, 1916-1922 (2013) and“ Viscoelasticity of Inhomogeneous Polymers Characterized by Loss Tangent Measurements Using Atomic Force Microscopy, macromolecules, 47, 7971-7977 (2014). It can be measured according to the method.

As an example, first, a test piece was obtained by slicing the crosslinked rubber product in the thickness direction, and the temperature was adjusted to 25 ° C. using an atomic force microscope in the range of 1 μm × 1 μm of the cross section of the obtained test piece. Then, the force volume measurement is performed with a resolution of 64 × 64 (resolution of 15.6 nm) to obtain an elastic modulus X at each measurement site. Then, for the obtained elastic modulus X at each measurement site, a histogram with the elastic modulus X on the horizontal axis and the frequency on the vertical axis is created, and the created histogram is analyzed by the Gaussian function to obtain the elastic modulus of the crosslinked rubber component. The mean value Xm and the standard deviation σ of are calculated. Then, the measurement site where Xm-2σ ≦ X ≦ Xm + 2σ is a crosslinked rubber component portion (of the crosslinked rubber components, which is substantially unaffected by the inorganic filler) among the crosslinked rubber components constituting the rubber crosslinked product. A portion sufficiently separated from the inorganic filler), that is, a non-interfacially formed crosslinked rubber component portion, while the measurement site where Xm + 3σ ≦ X ≦ Xm + 9σ is designated as an inorganic filling among the crosslinked rubber components constituting the rubber crosslinked product. It is specified as a crosslinked rubber component portion forming an interface with the agent, that is, an interface-forming crosslinked rubber component portion. Then, the area ratio of the non-interface-formed crosslinked rubber component portion to the total area of the specified non-interface-formed crosslinked rubber component portion and the interface-formed crosslinked rubber component portion was obtained, and this was defined as the ratio of the non-interface-formed crosslinked rubber component φ (m). , The area ratio of the interface-forming crosslinked rubber component portion is obtained, and this is calculated as the interface component ratio φ (i).

Next, for the test piece in which each measurement site was specified by the above method, vibration by a sine wave of 10 Hz was applied with an amplitude of 5 nm, and the same range was measured by using an atomic force microscope at 25 ° C., 64. By measuring the force volume with a resolution of × 64 (resolution of 15.6 nm), the amount of deformation and the phase delay of the test piece are measured, and the loss tangent value K at each measurement site is measured. Then, for the loss tangent value K at each measurement site, by calculating the average value for each of the non-interface-forming cross-linked rubber component portion and the interface-forming cross-linked rubber component portion specified above, the non-interface-forming cross-linked rubber component portion can be calculated. Loss tangent value, that is, the loss tangent value K (m) of the non-interface component forming a portion other than the interface with the inorganic filler, and the loss tangent value of the interface-forming cross-facial rubber component portion, that is, the interface with the inorganic filler. The loss tangent value K (i) of the interfacial component forming the above can be calculated, and from these, the ratio φ (m) of the non-interface component and the ratio φ (i) of the interfacial component obtained above can be calculated. The additive parameter AP (additive parameter AP = K (m) × φ (m) + K (i) × φ (i)) can be obtained. The identification of each measurement site and the measurement of the loss tangent values K (m) and K (i) may be performed separately or simultaneously.

Further, in the measurement using the atomic force microscope described above, the measurable resolution changes depending on the size of the probe used for the measurement. Therefore, in order to enable the measurement with the above resolution, the probe is a chip. It is preferable to use a probe having a radius of curvature of 1 to 100 nm (for example, a cantilever having such a radius of curvature of the tip), and it is more preferable to use a probe having a radius of curvature of 1 to 30 nm. As the cantilever, it is preferable to use a cantilever having a spring constant of 0.05 to 100 N / m, more preferably a cantilever having a spring constant of 0.2 to 40 N / m, and 0.5 to 5 N / m. It is even more preferable to use a cantilever. Further, as the cantilever, it is preferable to use a cantilever having a resonance frequency of 1 to 2000 kHz, more preferably a cantilever having a resonance frequency of 10 to 500 kHz, and further preferably using a cantilever having a resonance frequency of 40 to 100 kHz.

In the present invention, the method of setting the additive parameter AP (additive parameter AP = K (m) × φ (m) + K (i) × φ (i)) in the above range is not particularly limited, but rubber. The molecular weight of the conjugated diene-based rubber, the content ratio of the aromatic vinyl unit, the vinyl bond content in the conjugated diene monomer unit, and the modifying group to be introduced, which are used when preparing the rubber composition for forming the crosslinked product. A method of adjusting the type and introduction rate, a method of adjusting the blending amount and particle size of the inorganic filler used when preparing the rubber composition, a method of adjusting the kneading conditions when preparing the rubber composition, and further. , A method of adjusting the blending amount of the inorganic filler, and the like, and it is desirable to combine these appropriately.

Further, in the present invention, from the viewpoint that the wet grip property, low heat generation property and wear resistance of the obtained rubber crosslinked product can be further enhanced, in addition to setting the addability parameter AP in the above range, 10 Hz The ratio K (i) / K (m) of the loss tangent value K (m) of the non-interface component to the loss tangent value K (i) of the interface component when the vibration due to the sine wave of is applied is 0.80. It is preferably 0.75 or less, more preferably 0.73 or less, and particularly preferably 0.70 or less.

The method for producing the crosslinked rubber product of the present invention is not particularly limited, but using the above-mentioned rubber composition, for example, a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc. It can be manufactured by performing a cross-linking reaction by heating and fixing the shape as a cross-linked product. In this case, it may be crosslinked after being molded in advance, or may be crosslinked at the same time as molding. The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C., and the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 12 hours, particularly preferably 3 minutes to 6 hours. ..

Further, depending on the shape and size of the rubber crosslinked product, even if the surface is crosslinked, it may not be sufficiently crosslinked to the inside, so that it may be further heated for secondary crosslinking.

As the heating method, a general method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.

In the rubber crosslinked product of the present invention, the loss tangent value K (m) of the non-interface component and the ratio φ (m) of the non-interface component and the loss tangent value K of the interface component when vibration by a sine wave of 10 Hz is applied. The additive parameter AP (additive parameter AP = K (m) × φ (m) + K (i) × φ (i)) obtained from (i) and the ratio φ (i) of the interface component is 0. It is controlled to .36 or less, which is excellent in wet grip property, low heat generation property and abrasion resistance. The rubber crosslinked product of the present invention makes use of such characteristics, for example, in a tire, a material for each part of the tire such as a cap tread, a base tread, a carcass, a sidewall, and a bead portion; a hose, a belt, a mat, and a protective material. It can be used for various purposes such as oscillating rubber and other materials for various industrial products; resin impact resistance improving agents; resin film buffers; soles; rubber shoes; golf balls; toys. In particular, the crosslinked rubber product of the present invention is excellent in wet grip, low heat generation and wear resistance, and therefore can be suitably used as a material for tires, particularly fuel-efficient tires.

Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples. In the following, "part" is based on weight unless otherwise specified. The tests and evaluations were as follows.

[Molecular weight of conjugated diene rubber]
The molecular weight of the conjugated diene rubber was determined as a polystyrene-equivalent molecular weight by gel permeation chromatography. The specific measurement conditions are as follows.
Measuring instrument: High performance liquid chromatograph (manufactured by Tosoh Corporation, trade name "HLC-8320")
Column: Two Tosoh products, trade name "GMH-HR-H", were connected in series.
Detector: Differential refractometer (manufactured by Tosoh, trade name "RI-8320")
Eluent: tetrahydrofuran Column temperature: 40 ° C

[Microstructure of conjugated diene rubber]
¹ Measured by ¹ H-NMR.
Measuring instrument: (manufactured by JEOL Ltd., product name "JNM-ECA-400WB"
Measuring solvent: Deuterated chloroform

[Glass transition temperature of conjugated diene rubber]
The glass transition temperature (Tg) of the conjugated diene rubber was measured by differential scanning calorimetry (DSC) under the following conditions.
Measuring instrument: Pyris1 DSC (manufactured by PerkinElmer)
Heating rate: 10 ° C / min

[The loss tangent value K (m) of the non-interface component and the ratio φ (m) of the non-interface component, the loss tangent value K (i) of the interface component and the ratio φ (i) of the interface component, the additive parameter AP (K) (M) x φ (m) + K (i) x φ (i)), K (i) / K (m)]
After the rubber crosslinked product is extracted according to JIS K6229, the rubber crosslinked product after the extraction treatment is made of glass using Ultra Microtome (Leica EM UC7, manufactured by Leica Microsystems, Inc.) in an atmosphere of -100 ° C. Specimens were prepared by slicing in the thickness direction using a knife.

The obtained test piece is placed on a sample stage, and an atomic force microscope (manufactured by Bruker, product name "Dimension Icon AFM") is used for an area of 1 μm × 1 μm at any five points on the cross section of the test piece. By performing force volume measurement at 25 ° C. and scanning speed of 1 Hz with a resolution of 64 × 64 (resolution of 15.6 nm), the elastic modulus was measured through a cantilever as a measurement probe, and the elastic modulus was measured at 1 μm × 1 μm. An elastic modulus image in the viewing range of was obtained. In the measurement, a cantilever (manufactured by Olympus Corporation, product name "OMCL AC240-TS", spring constant 2 N / m, resonance frequency 70 kHz, chip radius of curvature 7 nm) was used as the measurement probe. Then, based on the elastic modulus image of the obtained test piece, a histogram having the elastic modulus X on the horizontal axis and the frequency on the vertical axis is created, and the created histogram is analyzed by the Gaussian function to obtain the elasticity of the crosslinked rubber component. The mean value Xm of the rate and the standard deviation σ were calculated. Then, the measurement site where the measured elastic modulus X is Xm-2σ ≦ X ≦ + Xm + 2σ is specified as a non-interface-forming crosslinked rubber component portion forming a portion other than the interface with silica, and is in the range of 1 μm × 1 μm. The area ratio of the non-interface cross-linked rubber component (the area ratio in the portion specified as the rubber component) was determined, and this was defined as the non-interface component ratio φ (m). Further, the measurement site where the measured elastic modulus X is Xm + 3σ ≦ X ≦ Xm + 9σ is specified as the interface-forming crosslinked rubber component portion forming the interface with silica, and the area of the interfacial crosslinked rubber component in the range of 1 μm × 1 μm. The ratio (the area ratio in the portion specified as the rubber component) was determined, and this was defined as the interface component ratio φ (i).

Next, for the same viewing range of the test piece, a lock-in amplifier (signal recovery) was used to attach a high-frequency band piezo actuator (manufactured by noliac, product name "NAC2011-A01") installed on the sample stage independently of the piezoelectric scanner. By driving with a 7280 type manufactured by the same company, an atomic force microscope (Bruker) is used for the test piece on the sample stage while independently generating vibrations due to a 10 Hz sinusoidal wave with an amplitude of 5 nm. According to the product name "Dimenceion Icon AFM"), the force volume measurement is performed at 25 ° C. at a scanning speed of 1 Hz and with a resolution of 64 x 64 (resolution of 15.6 nm), so that the amount of deformation of the test piece And the phase lag were measured through a cantilever as a measuring probe, thereby obtaining a loss tangent image due to a 10 Hz sinusoidal wave in a field range of 1 μm × 1 μm. In the measurement, a cantilever (manufactured by Olympus, product name "OMCL AC240-TS", spring constant 2 N / m, resonance frequency 70 kHz, chip curvature radius 7 nm) is used as a measurement probe, and the force volume is being measured. By introducing a resting time while the cantilever and the test piece were in contact with each other, the measurement was performed in a state where vibration by a 10 Hz sine wave was applied.

Then, for the loss tangent value K at each measurement site due to the 10 Hz sinusoidal wave, the non-interface is calculated by calculating the average value for each of the non-interface-formed cross-linked rubber component portion and the interface-formed cross-linked rubber component portion specified above. The loss tangent value of the formed cross-linked rubber component portion, that is, the loss tangent value K (m) of the non-interface component forming a portion other than the interface with silica, and the loss tangent value of the interface-formed cross-linked rubber component portion, that is, silica. After calculating the loss tangent value K (i) of the interface component forming the interface of, these, the ratio φ (m) of the non-interface component measured above, and the ratio φ (i) of the interface component are calculated. The additive parameter AP (additive parameter AP = K (m) × φ (m) + K (i) × φ (i)) was calculated using the product. At this time, the ratio K (i) / K (m) of the loss tangent value K (m) of the non-interface component and the loss tangent value K (i) of the interface component was also calculated.

[Wet grip]
A test piece of a rubber crosslinked product molded into a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm was subjected to a dynamic strain of 0.5% using a viscoelasticity measuring device (manufactured by Leometrics, product name "ARES"). Tan δ at 0 ° C. was measured under the condition of 10 Hz. The value of tan δ is shown as an index with the measured value of Comparative Example 1 as 100. The larger this index is, the better the wet grip property is.

[Low heat generation]
A test piece of a rubber crosslinked product molded into a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm was subjected to a dynamic strain of 2.5% using a viscoelasticity measuring device (manufactured by Leometrics, product name "ARES"). Tan δ at 60 ° C. was measured under the condition of 10 Hz. The value of tan δ is shown as an index with the measured value of Comparative Example 1 as 100. The smaller this index, the better the low heat generation.

[Abrasion resistance]
A test piece of a rubber crosslinked product molded into an outer diameter of 50 mm, an inner diameter of 15 mm, and a thickness of 10 mm was measured using an FPS wear tester (manufactured by Ueshima Seisakusho Co., Ltd.) at a load of 1 kgf and a slip ratio of 3%. This characteristic is shown by an index with the measured value of Comparative Example 1 as 100. The larger this index, the better the wear resistance.

[Example 1]
[Manufacture of Modified Conjugated Diene Rubber 1]
Under a nitrogen atmosphere, 800 g of cyclohexane, 71 g of 1,3-butadiene, 29 g of styrene, and 0.055 g of tetramethylethylenediamine were charged in an autoclave, 0.86 mmol of n-butyllithium was added, and polymerization was started at 60 ° C. did. After continuing the polymerization reaction for 60 minutes and confirming that the polymerization conversion rate was in the range of 95% to 100%, the modifier represented by the following formula (11) was added to the amount of n-butyllithium used. On the other hand, it was added in a state of a xylene solution having a concentration of 20% so as to be 0.05 times the molar amount, and after reacting for 30 minutes, 0.064 g of methanol was added as a polymerization inhibitor to add a conjugated diene rubber. The solution to be contained was obtained. Then, with respect to 100 g of the obtained polymer component, 0.15 g of 2,4-bis [(octylthio) methyl] -o-cresol (manufactured by Ciba Specialty Chemicals, trade name "Irganox 1520") as an antioxidant. Was added to the solution, the solvent was removed by steam stripping, and the mixture was vacuum dried at 60 ° C. for 24 hours to obtain a solid modified conjugated diene rubber 1. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 1 was 520,000. The styrene unit content of the modified conjugated diene rubber 1 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.9 ° C.

[Manufacturing of rubber compositions and crosslinked rubber products]
In a Brabender type mixer with a capacity of 250 ml, 100 parts of the modified conjugated diene rubber obtained above is kneaded for 30 seconds, then 23 parts of silica (manufactured by Solvay, trade name "Zeosil1165MP"), and a silane cup. Ring agent: Add 6.4 parts of bis (3- (triethoxysilyl) propyl) tetrasulfide (manufactured by Ebonic, trade name "Si69"), knead at 110 ° C. for 1.5 minutes, and then silica. (Manufactured by Solvay, trade name "Zeosil1165MP") 27 parts, zinc oxide 3 parts, stearic acid 2 parts and anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (large) Two parts (trade name "Nocrack 6C") manufactured by Uchishin Kagaku Kogyo Co., Ltd. were added and kneaded for another 2.5 minutes, and the kneaded product was discharged from the mixer. The temperature of the kneaded product at the end of kneading was 150 ° C. Then, the obtained kneaded product was cooled to room temperature and then kneaded again in a lavender type mixer for 2 minutes with 110 ° C. as a starting temperature, and then the kneaded product was discharged from the mixer. Next, in an open roll at 50 ° C., 1.5 parts of sulfur and a cross-linking accelerator: N-cyclohexyl-2-benzothiazolyl sulphenamide (trade name "Noxeller CZ-G", Ouchi) were added to the obtained kneaded product. After adding 1.8 parts (manufactured by Shinko Kagaku Kogyo Co., Ltd.) and 1.5 parts of cross-linking accelerator: 1,3-diphenylguanidine (trade name "Noxeller D", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) and kneading them. , The sheet-shaped rubber composition was taken out.
Next, the obtained rubber composition was press-crosslinked at 160 ° C. for 20 minutes to prepare a test piece of the rubber-crosslinked product, and the non-interface component when the test piece was vibrated by a 10 Hz sine wave. Loss tangent value K (m) and non-interface component ratio φ (m), interface component loss tangent value K (i) and interface component ratio φ (i), additive parameter AP (K (m) × φ (m) + K (i) × φ (i)) and K (i) / K (m) were measured, and wet grip, low heat generation and abrasion resistance were evaluated. The results are shown in Table 1.

[Example 2]
[Manufacture of modified conjugated diene rubber 2, rubber composition and crosslinked rubber]
The amount of tetramethylethylenediamine used was changed to 0.027 g, the amount of n-butyllithium used was changed to 0.52 mmol, and the same procedure as in Example 1 was performed to solidify the modified conjugated diene rubber 2 Got The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 2 was 1,020,000. The content of the styrene unit of the modified conjugated diene rubber 2 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.8 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 2 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Example 3]
[Manufacture of modified conjugated diene rubber 3, rubber composition and crosslinked rubber]
Instead of the denaturing agent represented by the above formula (11), 0.23 g (1.5 times the molar amount of n-butyllithium used) of the denaturing agent represented by the following formula (12) is used with xylene. A solid modified conjugated diene rubber 3 was obtained in the same manner as in Example 1 except that it was used without dilution. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 3 was 510,000. The styrene unit content of the modified conjugated diene rubber 3 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.7 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 3 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Example 4]
[Manufacture of modified conjugated diene rubber 4, rubber composition and crosslinked rubber]
The amount of tetramethylethylenediamine used was changed to 0.0027 g, and the amount of n-butyllithium used was changed to 0.52 mmol, and 0.118 g (n-butyllithium) of the modifier represented by the above formula (12) was changed. A solid modified conjugated diene rubber 4 was obtained in the same manner as in Example 3 except that 1.5 times mol) was used without diluting with xylene. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 4 was 1,020,000. The content of the styrene unit of the modified conjugated diene rubber 4 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.8 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 4 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Example 5]
[Manufacture of modified conjugated diene rubber 5, rubber composition and crosslinked rubber]
Instead of the denaturant represented by the above formula (11), 0.304 g (1.5 times the molar amount of n-butyllithium used) of the denaturant represented by the following formula (13) was added with xylene. A solid modified conjugated diene rubber 5 was obtained in the same manner as in Example 1 except that it was used without dilution. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 5 was 530,000. The content of the styrene unit of the modified conjugated diene rubber 5 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.9 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 5 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Example 6]
[Manufacture of modified conjugated diene rubber 6, rubber composition and crosslinked rubber]
The amount of tetramethylethylenediamine used was changed to 0.0027 g, and the amount of n-butyllithium used was changed to 0.52 mmol, and 0.152 g (n-butyllithium) of the modifier represented by the following formula (13) was changed. A solid modified conjugated diene-based rubber 6 was obtained in the same manner as in Example 5 except that 1.5 times mol) was used without diluting with xylene. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 6 was 1,000,000. The styrene unit content of the modified conjugated diene rubber 6 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.9 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 6 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Example 7]
[Manufacture of modified conjugated diene rubber 7, rubber composition and crosslinked rubber]
Instead of the denaturing agent represented by the above formula (11), 0.48 g (1.5 times the molar amount of n-butyllithium used) of the denaturing agent represented by the following formula (14) was added with xylene. A solid modified conjugated diene rubber 7 was obtained in the same manner as in Example 1 except that it was used without dilution. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 7 was 530,000. The content of the styrene unit of the modified conjugated diene rubber 7 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.7 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 7 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Example 8]
[Manufacture of modified conjugated diene rubber 8, rubber composition and crosslinked rubber]
The amount of tetramethylethylenediamine used was changed to 0.0027 g, and the amount of n-butyllithium used was changed to 0.52 mmol, and 0.024 g (n-butyllithium) of the modifier represented by the above formula (14) was changed. A solid modified conjugated diene rubber 8 was obtained in the same manner as in Example 7 except that 1.5 times mol) was used without diluting with xylene. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 8 was 1,020,000. The styrene unit content of the modified conjugated diene rubber 8 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.8 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 8 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 1.

[Comparative Example 1]
[Manufacture of unmodified conjugated diene rubber 9, rubber composition and crosslinked rubber]
A solid unmodified conjugated diene rubber 9 was obtained in the same manner as in Example 1 except that the modifier represented by the above formula (11) was not blended. The weight average molecular weight (Mw) of the obtained unmodified conjugated diene rubber 9 was 520,000. The styrene unit content of the unmodified conjugated diene rubber 9 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.9 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the unmodified conjugated diene rubber 9 obtained above was used instead of the modified conjugated diene rubber 1. The evaluation was performed in the same manner. The results are shown in Table 2.

[Comparative Example 2]
[Manufacturing of unmodified conjugated diene rubber 10, rubber composition and crosslinked rubber]
A solid unmodified conjugated diene rubber 10 was obtained in the same manner as in Comparative Example 1 except that the amount of 1,3-butadiene used was changed to 60 g and the amount of styrene used was changed to 40 g. The weight average molecular weight (Mw) of the obtained unmodified conjugated diene rubber 10 was 530,000. The styrene unit content of the unmodified conjugated diene rubber 10 was 40% by weight, the vinyl bond content in the butadiene unit was 51 mol%, and the glass transition temperature was −0.5 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Comparative Example 1 except that the unmodified conjugated diene rubber 10 obtained above was used instead of the modified conjugated diene rubber 9. The evaluation was performed in the same manner. The results are shown in Table 2.

[Comparative Example 3]
[Manufacture of unmodified conjugated diene rubber 11, rubber composition and crosslinked rubber]
A solid unmodified conjugated diene was operated in the same manner as in Comparative Example 1 except that the amount of tetramethylethylenediamine used was changed to 0.027 g and the amount of n-butyllithium used was changed to 0.52 mmol. A rubber system 11 was obtained. The weight average molecular weight (Mw) of the obtained unmodified conjugated diene rubber 11 was 1,010,000. The styrene unit content of the unmodified conjugated diene rubber 11 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.7 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Comparative Example 1 except that the unmodified conjugated diene rubber 11 obtained above was used instead of the unmodified conjugated diene rubber 9. , The same evaluation was performed. The results are shown in Table 2.

[Comparative Example 4]
[Manufacture of modified conjugated diene rubber 12, rubber composition and crosslinked rubber]
Instead of the modifier represented by the above formula (11), 0.15 g of tetramethoxysilane as a modifier (1.5 times mol with respect to the amount of n-butyllithium used) was not diluted with xylene. Same as in Example 1 except that the amount of 1,3-butadiene used was changed to 60 g, the amount of styrene used was changed to 40 g, and the amount of tetramethylethylenediamine used was changed to 0.152 g. The operation was carried out to obtain a solid modified conjugated diene rubber 12. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 12 was 520,000. The styrene unit content of the modified conjugated diene rubber 12 was 40% by weight, the vinyl bond content in the butadiene unit was 51 mol%, and the glass transition temperature was −0.6 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 12 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 2.

[Comparative Example 5]
[Manufacture of modified conjugated diene rubber 13, rubber composition and crosslinked rubber]
Instead of the modifier represented by the above formula (11), 0.076 g of tetramethoxysilane as a modifier (1.5 times mol with respect to the amount of n-butyllithium used) was not diluted with xylene. The solid state was operated in the same manner as in Example 1 except that the amount of tetramethylethylenediamine used was changed to 0.027 g and the amount of n-butyllithium used was changed to 0.52 mmol. The modified conjugated diene rubber 13 of the above was obtained. The weight average molecular weight (Mw) of the obtained modified conjugated diene rubber 13 was 1,050,000. The styrene unit content of the modified conjugated diene rubber 13 was 29% by weight, the vinyl bond content in the butadiene unit was 44 mol%, and the glass transition temperature was -21.6 ° C.
Then, a rubber composition and a rubber crosslinked product were obtained in the same manner as in Example 1 except that the modified conjugated diene rubber 13 obtained above was used instead of the modified conjugated diene rubber 1. Was evaluated. The results are shown in Table 2.

From Tables 1 and 2, the loss tangent value K (m) of the non-interface component and the ratio φ (m) of the non-interface component and the loss tangent value K of the interface component when vibration by a 10 Hz sine wave is applied, The additive parameter AP (additive parameter AP = K (m) × φ (m) + K (i) × φ (i)) calculated from i) and the ratio φ (i) of the interface component is 0. All of the rubber cross-linked products having a value of 360 or less were excellent in wet grip property, low heat generation property and abrasion resistance (Examples 1 to 8).
On the other hand, when the additivity parameter AP (addition parameter AP = K (m) × φ (m) + K (i) × φ (i)) is larger than 0.36, it has wet grip and low heat generation. And was inferior in wear resistance (Comparative Examples 1 to 5).

Claims (9)

A rubber crosslinked product obtained by cross-linking a rubber composition containing a conjugated diene-based rubber and an inorganic filler.
Among the crosslinked rubber components, other than the interface with the inorganic filler when the loss tangent is measured using an atomic force microscope in a state where the rubber crosslinked product is vibrated by a 10 Hz sinusoidal wave. The loss tangent value K (m) of the non-interface component forming the portion, the ratio φ (m) of the non-interface component, and the loss tangent value K of the interface component forming the interface with the inorganic filler among the cross-linked rubber components. A rubber crosslinked product characterized in that the value of the additive parameter obtained from (i) and the ratio φ (i) of the interface component according to the following formula (A) is 0.36 or less.
Additivity parameter = K (m) x φ (m) + K (i) x φ (i) (A)
(However, φ (m) + φ (i) = 1) The rubber crosslinked product according to claim 1, wherein the conjugated diene rubber is a modified conjugated diene rubber having a modifying group. The rubber crosslinked product according to claim 2, wherein the conjugated diene rubber is a modified conjugated diene rubber having a modifying group derived from a silicon atom-containing modifier. The rubber crosslinked product according to claim 3, wherein the conjugated diene-based rubber is a modified conjugated diene-based rubber having a modifying group derived from a siloxane compound or a nitrogen-containing silane compound. The rubber crosslinked product according to any one of claims 1 to 4, wherein the glass transition temperature (Tg) of the conjugated diene rubber is -40 to -10 ° C. The rubber crosslinked product according to any one of claims 1 to 5, wherein the vinyl bond content in the conjugated diene monomer unit in the conjugated diene rubber is 0 to 70 mol%. The rubber crosslinked product according to any one of claims 1 to 6, wherein the content of the inorganic filler is 10 to 200 parts by weight with respect to 100 parts by weight of the rubber component containing the conjugated diene rubber in the rubber composition. .. The rubber crosslinked product according to any one of claims 1 to 7, wherein the inorganic filler is silica. A tire comprising the crosslinked rubber product according to any one of claims 1 to 8.