JP6423610B2 - Rubber composition and pneumatic tire - Google Patents

Description

  The present invention relates to a rubber composition and a pneumatic tire.

  In recent years, there has been an increasing need for pneumatic tires having high motion performance such as acceleration performance and brake performance. In order to obtain such a high-performance pneumatic tire, it is an effective technique to improve grip performance such as dry grip performance.

Conventionally, in order to obtain high grip performance, there is known a method of improving grip performance by adding a certain resin to enhance adhesion between a rubber and a road surface.
In general, as the grip performance of the resin is higher, the adhesion with the metal mixer and the metal roll existing in the manufacturing process is higher, and the factory workability tends to be hindered.

  For such a problem, in Patent Document 1, by blending a specific resin and metal salt in the rubber composition, without impairing various performances of the tire such as fracture characteristics and wear resistance and factory workability, A tire capable of greatly improving grip performance as compared with a conventional one is disclosed.

JP 2007-217543 A

However, as a result of studies by the present inventors, the following has been found.
That is, (i) the rubber component in the rubber composition is nonpolar, while the metal salt is polar, so that the metal salt is difficult to disperse in the rubber and the metal salt is easily separated from the rubber. (Ii) Furthermore, since the metal salt tends to be separated from the rubber, a part of the metal salt may be exposed on the rubber surface. And (iii) When a part of metal salt is exposed in the joint part of a tread rubber, it will become difficult for rubber | gum to adhere | attach the exposed part of a metal salt.

  For this reason, in the pneumatic tire using a rubber composition containing a specific resin and a metal salt for a rubber member such as a tread rubber, the inventor increases the rubber peeling resistance (rubber tackiness) by It has been found that the adhesive strength of the entire joint portion of the rubber using the rubber composition can be further increased.

An object of the present invention is to provide a rubber composition capable of simultaneously obtaining high grip performance and high peel resistance of a pneumatic tire.
Moreover, an object of this invention is to provide the pneumatic tire provided with the high grip performance and the high peeling resistance simultaneously.

The rubber composition according to the present invention is characterized by containing a rubber component, at least one compound represented by the following general formula (I), and a silane coupling agent.
MX (I)
Wherein M is a metal cation selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, aluminum, iron, copper, tin, titanium, vanadium and manganese. And X is a counter ion of the cation.)
According to this configuration, it is possible to provide a rubber composition that can simultaneously obtain high grip performance and high peel resistance of a pneumatic tire.

In the rubber composition according to the present invention, the silane coupling agent is preferably a silane coupling agent represented by the following general formula (II).
^{R 1 xR 2 yR 3 zSi-} R 4 -S-CO-R 5 (II)
Wherein R ¹ is R ⁶ O—, R ⁶ C (═O) O—, R ⁶ R ⁷ C═NO—, R ⁶ R ⁷ NO—, R ⁶ R ⁷ N—, and — (OSiR ⁶ R ⁷ ) _n (OSiR ⁵ R ⁶ R ⁷ ); R ⁶ and R ⁷ are each independently an alkyl group, a cycloalkyl group having 1 to 18 carbon atoms, A group selected from an alkenyl group, a cycloalkenyl group, and an aryl group, and n is 0 to 10;
R ² is a hydrogen atom and an atom or group having 1 to 18 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an aryl group;
R ³ is a group represented by — [O (R ⁸ O) _m ] _0.5 —, and R ⁸ is selected from an alkylene group and a cycloalkylene group having 1 to 18 carbon atoms. A group, m is 1 to 4;
x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦ z ≦ 1;
R ⁴ is a group having 1 to 18 carbon atoms and selected from an alkylene group, a cycloalkylene group, a cycloalkylalkylene group, an alkenylene group, an arylene group, and an aralkylene group;
R ⁵ is a group having 1 to 18 carbon atoms and selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. )
Thereby, higher peeling resistance can be obtained without impairing workability (factory workability) of rubber kneading.

In the rubber composition according to the present invention, the total amount of the silane coupling agent is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the rubber component.
Thereby, it is easy to obtain high grip performance and high peeling resistance.

The rubber composition according to the present invention further includes a phenol resin, a terpene phenol resin, a C5 petroleum resin, a C9 petroleum resin, a C5 / C9 copolymer resin, a dicyclopentadiene (DCPD) resin, and these modified resins. It is preferable to contain at least one resin R selected from the group consisting of resins.
Thereby, grip performance can be improved more.

In the rubber composition according to the present invention, the modified C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymer resin and dicyclopentadiene (DCPD) resin are a hydroxyl group, a carbonyl group, a carboxyl group, By a compound having at least one functional group selected from the group consisting of ester bond (—COO—), alkoxy group, amino group, nitro group, halogen group, amide group, nitrile group, sulfone group, thiol group and sulfide group A modified resin is preferred.
Thereby, grip performance can be improved more.

In the rubber composition according to the present invention, the total amount of the resin R is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
Thereby, it is easy to obtain high grip performance and high peel resistance, and grip performance and factory workability in a low temperature region are also improved.

In the rubber composition according to the present invention, the compound represented by the general formula (I) is preferably magnesium oxide.
Thereby, grip performance can be further improved.

The pneumatic tire according to the present invention is characterized in that the rubber composition is used for a tread rubber.
Thereby, high grip performance and high peeling resistance can be provided at the same time.

ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which can obtain simultaneously the high grip performance and high peeling resistance of a pneumatic tire can be provided.
An object of the present invention is to provide a pneumatic tire having high grip performance and high peel resistance at the same time.

It is sectional drawing which showed typically an example of the pneumatic tire which concerns on this invention.

(Rubber composition)
The rubber composition according to the present invention is characterized by containing a rubber component, at least one compound represented by the following general formula (I), and a silane coupling agent.
MX (I)
Wherein M is a metal cation selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, aluminum, iron, copper, tin, titanium, vanadium and manganese. And X is a counter ion of the cation.)
Hereinafter, each component of the rubber composition according to the present invention will be exemplified and described in order. These descriptions are intended to exemplify the present invention and do not limit the present invention in any way.

<Rubber component>
It does not specifically limit as a rubber component, The rubber component used for the conventionally well-known tire rubber composition can be used.
Examples of the rubber component include natural rubber; styrene butadiene rubber; butadiene rubber; isoprene rubber (synthetic isoprene); butyl rubber; halogenated butyl rubber such as chlorobutyl and bromobutyl; ethylene-propylene-diene rubber (EPDM).
You may use a rubber component individually by 1 type or in combination of 2 or more types.

<Compound represented by formula (I)>
In the present invention, the compound represented by the general formula (I) is a component that contributes to improvement of grip performance.
Where M is a cation of a metal selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, aluminum, iron, copper, tin, titanium, vanadium and manganese. .
X is a counter ion of the cation, and examples thereof include, but are not limited to, an oxygen atom, a sulfur atom, a halogen atom, a hydroxyl group, carbonic acid, sulfuric acid, and stearic acid.

  As the compound represented by the general formula (I), when M is lithium, for example, lithium chloride, lithium benzoate, lithium formate, lithium citrate, lithium acetate, lithium bromide, lithium oxalate, lithium nitrate, water Lithium oxide, lithium hydride, lithium stearate, lithium carbonate, lithium dodecyl sulfate, lithium lactate, lithium pyruvate, lithium fluoride, lithium hexafluorophosphate, lithium tetraborate, lithium sulfate, lithium phosphate, lithium iodide However, it is not limited to these.

  As the compound represented by the general formula (I), when M is sodium, for example, sodium chlorite, sodium nitrite, sodium azide, sodium sulfite, sodium benzoate, sodium alginate, sodium chloride, sodium chlorate, Sodium oleate, sodium formate, sodium citrate, sodium glycolate, sodium gluconate, sodium succinate, sodium salicylate, sodium bromide, sodium oxalate, sodium nitrate, sodium hydroxide, sodium hydride, sodium stearate, Examples include, but are not limited to, sodium carbonate, sodium bicarbonate, sodium lactate, sodium fluoride, sodium borate, sodium sulfate, sodium phosphate, sodium iodide and the like.

  As the compound represented by the general formula (I), when M is potassium, for example, potassium nitrite, potassium sulfite, potassium benzoate, potassium chloride, potassium chlorate, potassium oleate, potassium formate, potassium citrate, glucone Potassium acid, potassium silicate, potassium succinate, potassium acetate, potassium bromide, potassium oxalate, potassium bromate, potassium nitrate, potassium hydroxide, potassium hydride, potassium stearate, potassium carbonate, potassium bicarbonate, potassium lactate, Examples thereof include, but are not limited to, potassium fluoride, potassium borate, potassium sulfate, potassium phosphate, potassium iodide and the like.

  Examples of the compound represented by the general formula (I) include, but are not limited to, when M is rubidium, for example, rubidium chloride, rubidium nitrate, rubidium hydroxide, rubidium carbonate, and rubidium iodide.

  As the compound represented by the general formula (I), when M is cesium, examples thereof include cesium azide, cesium chloride, cesium nitrate, cesium hydroxide, cesium carbonate, cesium fluoride, cesium iodide, cesium nitrate and the like. However, it is not limited to these.

  Examples of the compound represented by the general formula (I) include, but are not limited to, beryllium oxide, beryllium chloride, beryllium sulfate, beryllium nitrate, and beryllium sulfide when M is beryllium.

  As the compound represented by the general formula (I), when M is magnesium, for example, magnesium oxide, magnesium hydroxide, magnesium acetate, magnesium hydrogen sulfate, magnesium sulfate, magnesium fluoride, magnesium chloride, magnesium bromide, iodide Magnesium, magnesium carbonate, magnesium bicarbonate, magnesium benzoate, magnesium chromate, magnesium phosphate, magnesium hydrogen phosphate, magnesium nitrate, magnesium lactate, magnesium oxalate, magnesium perchlorate, magnesium stearate, magnesium succinate, sulfide Although magnesium etc. are mentioned, it is not limited to these.

  As the compound represented by the general formula (I), when M is calcium, for example, calcium oxide, calcium hydroxide, calcium sulfate, calcium acetate, calcium benzoate, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, diphosphate phosphate Calcium hydrogen, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium citrate, calcium formate, calcium gluconate, calcium glycerophosphate, calcium phosphinate, calcium lactate, calcium molybdate, calcium nitrate, calcium nitrite , Calcium oleate, calcium oxalate, calcium palmitate, calcium peroxide, calcium propionate, calcium silicate, calcium stearate, calcium tartrate, calcium thiocyanate Siumu, calcium tungstate, calcium pantothenate, but like calcium sulfide, and the like.

  As the compound represented by the general formula (I), when M is strontium, for example, strontium acetate, strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium carbonate, strontium formate, strontium hydroxide, oxidation Examples include, but are not limited to, strontium, strontium nitrate, strontium oxalate, strontium sulfate, and strontium sulfide.

  As the compound represented by the general formula (I), when M is barium, barium acetate, barium aluminate, barium borate, barium fluoride, barium chloride, barium bromide, barium iodide, barium carbonate, barium chlorate , Barium chromate, barium phosphate, barium hydrogen phosphate, barium hydroxide, barium lactate, barium molybdate, barium nitrate, barium oxalate, barium perchlorate, barium peroxide, barium stearate, barium sulfate, barium sulfite , Barium thiocyanate, barium thiosulfate, barium titanate, barium sulfide and the like.

  As the compound represented by the general formula (I), when M is radium, for example, radium oxide, radium hydroxide, radium fluoride, radium chloride, radium bromide, radium iodide, radium carbonate, radium sulfate, radium sulfide. However, it is not limited to these.

  As the compound represented by the general formula (I), when M is aluminum, for example, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum bromide, aluminum acetate, aluminum sulfate, aluminum borate, aluminum iodide, aluminum lactate , Aluminum laurate, aluminum nitrate, aluminum oleate, aluminum phosphate, aluminum fluoride, and the like.

  As the compound represented by the general formula (I), when M is iron, for example, iron oxide, iron hydroxide, iron fluoride, iron chloride, iron bromide, iron iodide, iron lactate, iron nitrate, iron sulfate , Iron sulfide, iron acetate and the like, but are not limited thereto.

  As the compound represented by the general formula (I), when M is copper, for example, copper oxide, copper hydroxide, copper sulfate, copper acetate, copper chloride, copper fluoride, copper bromide, copper iodide, copper carbonate , Copper naphthenate, copper oleate, copper oxalate, copper phosphate, copper nitrate, copper stearate and the like, but are not limited thereto.

  Examples of the compound represented by the general formula (I) include, when M is tin, tin oxide, tin hydroxide, tin fluoride, tin chloride, tin bromide, tin iodide, tin oxalate and the like. However, it is not limited to these.

  Examples of the compound represented by the general formula (I) include, but are not limited to, titanium oxide, titanium chloride, titanium sulfate and the like when M is titanium.

  Examples of the compound represented by the general formula (I) include, but are not limited to, vanadium oxide and vanadium sulfate when M is vanadium.

  As the compound represented by the general formula (I), when M is manganese, for example, manganese oxide, manganese sulfate, manganese bromide, manganese acetate, manganese benzoate, manganese carbonate, manganese chloride, manganese oxalate, manganese nitrate, etc. However, it is not limited to these.

In one embodiment of the rubber composition according to the present invention, M of the compound represented by the general formula (I) is preferably magnesium or calcium from the viewpoint of grip performance.
In another embodiment of the rubber composition according to the present invention, the compound represented by the general formula (I) is composed of magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, and calcium carbonate from the viewpoint of grip performance. It is preferably at least one selected from the group.
In another embodiment of the rubber composition according to the present invention, the compound represented by the general formula (I) is more preferably magnesium oxide. Thereby, grip performance can be further improved.

  The compounds represented by the general formula (I) may be used singly or in combination of two or more.

  Although the total compounding quantity of the compound represented by general formula (I) is not specifically limited, What is necessary is just to adjust suitably, For example, it is preferable that it is 0.01-20 mass parts with respect to 100 mass parts of rubber components. . By setting it as 0.01 mass part or more, it is easy to acquire the sufficient effect which improves grip performance. Moreover, 20 mass parts or less are preferable from a viewpoint of cost performance.

<Silane coupling agent>
In the present invention, the silane coupling agent is a component that contributes to an improvement in peeling resistance.
Although not wishing to be bound by theory, the reason why a high peel resistance can be obtained by the silane coupling agent is that the silane coupling agent covers the surface of the compound represented by the general formula (I), and the compound This is presumably because the tackiness of the rubber is maintained by preventing the rubber from being exposed to the surface of the rubber or suppressing the exposure.

In the rubber composition according to the present invention, the silane coupling agent is preferably a silane coupling agent represented by the following general formula (II).
^{R 1 xR 2 yR 3 zSi-} R 4 -S-CO-R 5 (II)
Wherein R ¹ is R ⁶ O—, R ⁶ C (═O) O—, R ⁶ R ⁷ C═NO—, R ⁶ R ⁷ NO—, R ⁶ R ⁷ N—, and — (OSiR ⁶ R ⁷ ) _n (OSiR ⁵ R ⁶ R ⁷ ); R ⁶ and R ⁷ are each independently an alkyl group, a cycloalkyl group having 1 to 18 carbon atoms, A group selected from an alkenyl group, a cycloalkenyl group, and an aryl group, and n is 0 to 10;
R ² is a hydrogen atom and an atom or group having 1 to 18 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an aryl group;
R ³ is a group represented by — [O (R ⁸ O) _m ] _0.5 —, and R ⁸ is selected from an alkylene group and a cycloalkylene group having 1 to 18 carbon atoms. A group, m is 1 to 4;
x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦ z ≦ 1;
R ⁴ is a group having 1 to 18 carbon atoms and selected from an alkylene group, a cycloalkylene group, a cycloalkylalkylene group, an alkenylene group, an arylene group, and an aralkylene group;
R ⁵ is a group having 1 to 18 carbon atoms and selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. )
Thereby, the tackiness of rubber can be maintained and higher peeling resistance can be obtained without impairing the workability of rubber kneading.

In R ⁶ and R ⁷ , the alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
In R ⁶ and R ⁷ , examples of the cycloalkyl group include a cyclohexyl group and an ethylcyclohexyl group.
In R ⁶ and R ⁷ , examples of the alkenyl group include a vinyl group, an allyl group, and a methanyl group.
In R ⁶ and R ⁷ , examples of the cycloalkenyl group include a cyclohexenyl group and an ethylcyclohexenyl group.
In R ⁶ and R ⁷ , examples of the aryl group include a phenyl group and a tolyl group.

In R ² , each group is the same as those groups in R ⁶ and R ⁷ above.

In R ⁸ , the alkylene group may be linear or branched. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group.
In R ⁸ , examples of the cycloalkylene group include a cyclohexylene group.

In the R ³ , the — [O (R ⁸ O) _m ] _0.5 — group includes, for example, a 1,2-ethanedioxy group, a 1,3-propanedioxy group, a 1,4-butanedioxy group, 1, 5-pentanedioxy group, 1,6-hexanedioxy group and the like can be mentioned.

In R ⁴ , the alkylene group and cycloalkylene group are the same as those in R ⁸ .
In R ⁴ , examples of the cycloalkylalkylene group include a cyclohexylmethylene group.
In R ⁴ , the alkenylene group may be linear or branched. Examples of the alkenylene group include a vinylene group and a propenylene group.
In R ⁴ , examples of the arylene group include a phenylene group.
In R ⁴ , examples of the aralkylene group include a xylylene group.

In R ⁵ , the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, and aryl group are the same as those groups in R ⁶ and R ⁷ above.
In R ⁵ , examples of the aralkyl group include a benzyl group and a phenethyl group.

The silane coupling agent represented by the general formula (II) can be synthesized, for example, by the method described in JP-T-2001-505225.
Moreover, as said silane coupling agent, you may use commercial items, such as brand name ABC-856 by Shin-Etsu Chemical Co., Ltd., for example.

  The total amount of the silane coupling agent is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the rubber component. By being 1 part by mass or more, it is easy to obtain high grip performance and high peel resistance. From the viewpoint of cost performance, 15 parts by mass or less is preferable.

<Other ingredients>
In addition to the rubber component, the compound represented by the general formula (I), and the silane coupling agent, the rubber composition according to the present invention contains a resin R described later in order to improve grip performance. Also good.
Further, the rubber composition according to the present invention includes conventionally known oils, stearic acid, vulcanizing agents, vulcanization accelerators, anti-aging agents, and scorch preventing agents used in rubber compositions for pneumatic tires. Components such as an agent may be added.
Hereinafter, the resin R effective for improving the grip performance will be described.

<Resin R>
The rubber composition according to the present invention further includes a phenol resin, a terpene phenol resin, a C5 petroleum resin, a C9 petroleum resin, a C5 / C9 copolymer resin, a dicyclopentadiene (DCPD) resin, and these modified resins. It is preferable to contain at least one resin R selected from the group consisting of resins. Thereby, it is easy to improve grip performance.

As a phenol resin, arbitrary phenol resins, such as a novolak type and a resol type, can be used.
Specific examples of the monomer of the phenol resin include, but are not limited to, phenol, alkylphenols such as cresol, and resole. Specific examples of monomers copolymerized with these monomers include, but are not limited to, formaldehyde, acetylene, ethylene and the like.
As the phenol resin, a resin obtained by polymerizing phenol having an alkyl group having 2 to 9 carbon atoms and another organic compound, and having a degree of polymerization of the resin of 10 or less is preferably used. be able to. As the phenol resin, pt-butylphenol-formaldehyde resin and pt-butylphenol-acetylene resin are preferable, and pt-butylphenol-acetylene resin is more preferable.

As the terpene phenol resin, for example, α-pinene phenol resin, dipentene phenol resin, terpene bisphenol resin, or a hydrogenated product of these can be used.
In addition, as the terpene phenol resin, commercially available products such as trade name YS Polystar T145 and trade name YS Polystar T160 manufactured by Yasuhara Chemical Co., Ltd. may be used.

C5 petroleum resin is a resin of C5 fraction obtained by thermal decomposition of naphtha.
Examples of the C5 fraction include olefinic hydrocarbons and diolefinic hydrocarbons.
Examples of the olefinic hydrocarbon of the C5 fraction include 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene.
Examples of the diolefin hydrocarbon of the C5 fraction include 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 3-methyl-1,2-butadiene and the like.
In addition, as the C5-based petroleum resin, commercially available products such as trade name “Stractol TS30” manufactured by Straktor and trade name “TX-500” manufactured by Mitsui Chemicals, Inc. may be used.

The C9 petroleum resin is a C9 fraction resin obtained by thermal decomposition of naphtha.
Examples of the C9 fraction include styrene homologues such as α-methylstyrene, β-methylstyrene, and γ-methylstyrene; and indene homologues such as indene and coumarone.
Other examples of the C9 petroleum resin include trade name Nisseki Neopolymer manufactured by JX Nippon Oil & Energy Corporation.

  Examples of the C5 / C9 copolymer resin include a copolymer of the C5 fraction and the C9 fraction.

  Examples of the DCPD resin include Quantone (registered trademark) 1000 series such as trade name Quantone (registered trademark) 1105 manufactured by Nippon Zeon Co., Ltd.

The above-described phenol resin, terpene phenol resin, C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymer resin, and DCPD resin may be modified resins.
In the rubber composition according to the present invention, the modified C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymer resin and DCPD resin are a hydroxyl group, a carbonyl group, a carboxyl group, an ester bond (—COO A resin modified with a compound having at least one functional group selected from the group consisting of-), alkoxy group, amino group, nitro group, halogen group, amide group, nitrile group, sulfone group, thiol group and sulfide group; Preferably there is. Thereby, it is easy to improve grip performance.

  In the rubber composition according to the present invention, the modified resin may be a resin modified by at least one of phenol modification, maleic acid modification, and carboxylic acid modification.

  In the rubber composition according to the present invention, examples of the modified phenol resin include rosin-modified and / or cashew-modified resins.

  In the rubber composition according to the present invention, the total amount of the resin R is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the rubber component. By being 0.1 mass part or more, it is easy to obtain high grip performance and high peeling resistance. By being 100 parts by mass or less, grip performance and factory workability in a low temperature region (a temperature region other than a high temperature region during traveling, for example, −30 ° C. to room temperature (25 ° C.)) are also improved.

In addition, instead of the resin R, a reaction product of the compound represented by the general formula (I) and the resin R may be blended in the rubber composition according to the present invention. The reactant can be obtained, for example, by the following method.
First, after the resin R is dissolved in an organic solvent such as toluene, hexane, cyclohexane, tetrahydrofuran (THF), acetone, benzene, etc., the compound represented by the general formula (I) is added and stirred for several minutes to several days. To do. Thereafter, the reaction product can be obtained by performing filtration and removing the solvent from the filtrate.
Moreover, the said reaction material can also be obtained by mixing and making the compound represented by the said general formula (I) react with the resin R heated up to the temperature more than a softening point, or the resin R of a molten state. Examples of the temperature raising method include a method of kneading a resin with a pressure kneader.

  The rubber composition according to the present invention can be prepared by kneading the aforementioned components using a kneader such as an open kneader such as a roll or a closed kneader such as a Banbury mixer.

<Use of rubber composition>
The rubber composition according to the present invention can be used for tire members such as treads, carcass, sidewalls, beads, and the like because it can simultaneously obtain high grip performance and high peel resistance of a pneumatic tire. It can be suitably used for a tread.
For example, when the rubber composition according to the present invention is used for the tread rubber, the adhesion resistance of the joint portion of the last tread rubber when the tread rubber is wound along the rolling direction of the tire at the time of manufacturing the tire is excellent.

(Pneumatic tire)
The pneumatic tire according to the present invention is characterized in that the rubber composition is used for a tread rubber. Thereby, high grip performance and high peeling resistance can be obtained simultaneously.

  FIG. 1 is a cross-sectional view showing an example of a pneumatic tire according to the present invention. In an example of this pneumatic tire, a pair of bead portions 1, a pair of sidewall portions 2 that are continuous to the outside in the radial direction of the bead portion 1, and a tread portion 3 that straddles the sidewall portions 2. Become. A carcass 5 made of a carcass ply extending in a toroidal shape is arranged between the bead cores 4 of the bead part 1, and a belt 6 having three belt layers is arranged outside the tread part 3 of the carcass 5 in the radial direction. Thus, a tire skeleton is formed.

  The pneumatic tire according to the present invention can be produced by using the rubber composition as a tread rubber and vulcanizing according to a conventional method. The vulcanization temperature can be, for example, 100 to 190 ° C. The vulcanization time can be, for example, 5 to 80 minutes.

  The present invention will be described in more detail below with reference to examples, but these examples are intended to illustrate the present invention and do not limit the present invention in any way.

Details of each component of * 1 to * 12 in Table 1 and Table 2 are as follows.
* 1 Styrene-butadiene rubber (SBR): trade name Toughden (registered trademark) 4350 manufactured by Asahi Kasei Co., Ltd. (S-SBR, 39% bonded styrene content, 38% vinyl bond, 50 parts by weight relative to 100 parts by mass of rubber component) Oil exhibition with parts by weight of aromatic oil)
* 2 Compound represented by general formula (I): Reagent purchased from Kanto Chemical Co., Ltd. * 3 Silane coupling agent: Trade name ABC-856 manufactured by Shin-Etsu Chemical Co., Ltd.
* 4 Resin A (Resin R): Butylphenol acetylene condensate resin, trade name Cholecin * 5 manufactured by BASF * Resin B (Resin R): Novolak-type alkylphenol resin, trade name Hitanol 1502 manufactured by Hitachi Chemical Co., Ltd.
* 6 Resin C (Resin R): Aromatic petroleum resin, unmodified type, trade name Nisseki Neopolymer L90 manufactured by JX Nippon Mining & Energy Corporation
* 7 Resin D (Resin R): C9 petroleum resin, trade name Nisseki Neopolymer E130 manufactured by JX Nippon Oil & Energy Corporation
* 8 Carbon black: SAF (N ₂ SA: 150 m ² / g)
* 9 Process oil: Product name A / O MIX manufactured by JX Nippon Oil & Energy Corporation
* 10 Anti-aging agent: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine * 11 Vulcanization accelerator A: N- (tert-butyl) -2-benzothiazolesulfenamide * 12 Vulcanization accelerator B: Tetrakis (2-ethylhexyl) thiuram disulfide

(Examples 1 to 9, Reference Examples 10 to 15 and Comparative Examples 1 to 3)
The rubber compositions having the compounding recipes shown in Tables 1 and 2 below were kneaded using a Banbury mixer. And the pneumatic tire provided with the tread rubber which consists of an obtained rubber composition was produced.
About the produced pneumatic tire, as shown below, an actual vehicle dry grip, peeling resistance, and factory workability were evaluated. The results are also shown in Table 1 and Table 2.

(Actual dry grip performance)
Equipped with a high-performance vehicle capable of traveling at a maximum speed of 300 km / h with each of the tires produced, running on a dry road surface on a circuit, in the initial driving (measurement lap 1) grip and in the final ending grip of measurement lap 12 The test driver's feeling was evaluated according to the following criteria. It shows that dry grip performance is so favorable that the numerical value of the following reference | standard is large with a positive value.
[Evaluation criteria]
+3: Very good +2: Good +1: Somewhat good 0: Normal -1: Somewhat bad -2: Bad

(Peeling resistance)
The rubber composition was vulcanized under the conditions of 145 ° C. and 45 minutes in accordance with the method of JIS K6301, and the peak adhesion resistance was measured under an atmosphere of 100 ° C. The evaluation was expressed as an index with the peak adhesion resistance of Comparative Example 1 (control) as 100. It shows that peeling resistance is so large that a numerical value is large.

(Factory workability)
The unvulcanized rubber composition was wound around a roll at 80 ° C. for 1 minute or longer and cut with a roll knife. At that time, the amount adhered to the roll was weighed and evaluated according to the following criteria.
(Circle): The quantity closely_contact | adhered to the roll was less than 10 mass%.
(Triangle | delta): The quantity closely_contact | adhered to the roll was 10 mass% or more.

  The rubber composition according to the present invention contains a rubber component, a compound represented by the general formula (I), and a silane coupling agent, thereby simultaneously obtaining high grip performance and high peel resistance of a pneumatic tire. I was able to.

  The rubber composition according to the present invention can be suitably used in the manufacture of tire members (particularly, tire tread rubber).

1 Bead part 2 Side wall part 3 Tread part 4 Bead core 5 Carcass 6 Belt

Claims (3)

Rubber component,
And magnesium oxide,
A silane coupling agent;
Phenolic resin,
A pneumatic tire characterized by using a rubber composition (excluding a rubber composition containing silica) containing a tread rubber. The pneumatic tire according to claim 1 , wherein a total amount of the silane coupling agent in the rubber composition is 1 to 15 parts by mass with respect to 100 parts by mass of the rubber component. The pneumatic tire according to claim 1 or 2 , wherein a blending amount of the phenol resin in the rubber composition is 0.1 to 100 parts by mass with respect to 100 parts by mass of the rubber component.

Images