JP2009280699A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire compatible in excellent rolling resistance and good dry steering stability. <P>SOLUTION: The tire is characterized by using a rubber composition containing: (A) at least a kind of a rubber component selected from natural rubber and diene synthetic rubber; (B) an inorganic filler of 20-150 pts.mass and (C) a maleic acid or fumaric acid ester of polyhydric alcohol of 0.3-7 pts.mass to the component (A) of 100 pts.mass; and (D) a silane coupling agent including protected mercaptosilane having a specific structure, of 2-30 mass% to the inorganic filler of the component (B). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a tire using a specific rubber composition. More specifically, the present invention relates to a silane coupling agent comprising a mercaptosilane having a specific structure and containing a protected mercapto group (hereinafter referred to as “protected mercaptosilane”) and a polyvalent in an inorganic filler compounding system. The present invention relates to a tire, particularly a pneumatic tire, which uses a rubber composition containing an alcohol maleic acid or fumaric acid ester and can achieve both excellent rolling resistance and good dry handling stability.

In recent years, with the social demand for energy saving and the increasing interest in environmental issues, the demand for lower fuel consumption of automobiles has become more severe. In order to meet such demands, reduction in rolling resistance has also been demanded for the performance of passenger car tires and truck / bus tires. As a technique for reducing the rolling resistance of the tire, a technique by optimizing the tire structure has been studied, but the most common technique is to use a rubber composition having lower heat generation as the tread rubber layer. ing.
Numerous technological developments have been made to obtain such a low heat-generating rubber composition, but it is known that it is advantageous to make the tread rubber harder from the viewpoint of reducing energy loss. . However, in this case, the extrudability deteriorates and the workability during tire manufacture is adversely affected.
On the other hand, in recent years, with increasing interest in safety of automobiles, not only low fuel consumption performance, but also performance on wet road surfaces (hereinafter referred to as wet performance), particularly braking performance, has been increasing. For this reason, the performance requirement for the rubber composition of the tire tread is not limited to merely reducing the rolling resistance, but it is required to have a high balance between wet performance and low fuel consumption performance.

As a method of obtaining a rubber composition that gives tires good fuel economy and good wet performance at the same time, as a filler for reinforcement, silica or the like instead of carbon black that has been generally used so far A method using an inorganic filler has already been carried out.
However, silica tends to aggregate particles due to hydrogen bonding of silanol groups which are surface functional groups, and silica particles are not sufficiently dispersed in rubber. Various alkoxysilanes have been used as silica surface treatment agents or coupling agents by utilizing the condensation reaction with alkoxysilanes. For example, recently, protected mercaptosilanes such as acylthioalkyltrialkoxysilanes have been developed as silane coupling agents (see, for example, Patent Document 1). This protected mercaptosilane has the effect of improving the dispersibility of silica in the rubber composition, improving the workability and improving the rolling resistance performance, but reduces the dry handling stability. Have a problem.
As a method for improving the handling stability without impairing the fuel economy of the inorganic filler-containing rubber such as silica, a method of adding a resin is known (see, for example, Patent Document 2 and Patent Document 3). The compatibility between the resin and the rubber is insufficient, and there are problems such as surface roughness of the vulcanized rubber.

Special table 2001-505225 gazette JP 2000-80205 A JP 2000-290433 A

  An object of the present invention is to provide a tire capable of achieving both excellent rolling resistance and good dry steering stability under such circumstances.

[式中、Ｒ⁶は炭素数１〜２０の直鎖もしくは、分岐、環状のアルキル基であり、Ｇはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基であり、Ｚ^aはそれぞれ独立して二つの珪素原子と結合することのできる基で、 [−０−]_0.5、[−０−Ｇ−]_0.5又は[−Ｏ−Ｇ−Ｏ−] _0.5から選ばれる基であり、Ｚ^bはそれぞれ独立して二つの珪素原子と結合することのできる基で、 [−Ｏ−Ｇ−Ｏ−] _0.5で表される官能基であり、Ｚ^cはそれぞれ独立して−Ｃｌ、−Ｂｒ、−ＯＲ⁷、Ｒ⁷Ｃ(＝Ｏ)Ｏ−、Ｒ⁷Ｒ⁸Ｃ＝ＮＯ−、Ｒ⁷Ｒ⁸Ｎ−，Ｒ⁷−，ＨＯ−Ｇ−Ｏ−で表される官能基であり、Ｇは上記表記と一致し、Ｒ⁷及びＲ⁸はそれぞれ独立に炭素数１〜２０の直鎖もしくは、分岐、環状のアルキル基である。
ｍ、ｎ、ｕ、ｖ、ｗはそれぞれ独立して１≦ｍ≦２０、０≦ｎ≦２０、０≦ｕ≦３、０≦ｖ≦２、０≦ｗ≦１であり、かつ（ｕ／２）＋ｖ＋２ｗ＝２又は３である。
Ａ部が複数である場合、複数のＡ部におけるＺ^a _u、Ｚ^b _v及びＺ^c _wそれぞれにおいて
、同一でも異なっていてもよく、Ｂ部が複数である場合、複数のＢ部におけるＺ^a _u、Ｚ^b _v及びＺ^c _wそれぞれにおいて、同一でも異なってもよい。]
で表されるシランカップリング剤を、前記（Ｂ）成分の無機充填材に対して２〜３０質量％の割合で含むゴム組成物を用いることを特徴とするタイヤ、
［２］前記一般式（II）で表される（Ｄ）成分が、化学式（III）、

化学式（ＩV）、

及び化学式（V）

［式中、Ｌはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基であり、ｘ＝ｍ、ｙ＝ｎである。］で表されるシランカップリング剤の中から選ばれる少なくとも一種である上記［１］に記載のタイヤ、
［３］前記無機充填材がシリカである上記［１］又は［２］に記載のタイヤ、
［４］（Ａ）ゴム成分１００質量部に対し、（Ｂ）無機充填材４０〜９０質量部を含む上記［１］〜［３］のいずれかに記載のタイヤ、
［５］さらに、（Ｅ）カーボンブラックを、（Ａ）ゴム成分１００質量部に対し、５〜４０質量部の割合で含む上記［１］〜［４］のいずれかに記載のタイヤ、
［６］（Ｃ）成分の一般式（Ｉ）で表される化合物が、ポリエチレングリコールジマレエート又はポリエチレングリコールジフマレートである上記［１］〜［５］のいずれかに記載のタイヤ、及び
［７］前記ゴム組成物をトレッドに用いてなる上記［１］〜［６］のいずれかに記載のタイヤ、
を提供するものである。 As a result of intensive studies to achieve the above object, the present inventors have identified natural rubber and / or diene synthetic rubber as inorganic fillers such as silica and maleic acid or fumaric acid ester of polyhydric alcohol. It was found that the object can be achieved by using, for a tire, a rubber composition obtained by blending each of the above silane coupling agents in a predetermined ratio. The present invention has been completed based on such findings.
That is, the present invention
[1] (B) 20 to 150 parts by mass of inorganic filler and (C) general formula (A) with respect to 100 parts by mass of (A) at least one rubber component selected from natural rubber and diene-based synthetic rubber I)
HOOC-CH = CH-COO- A 1 -OOC-CH = CH-COOH ··· (I)
[Wherein, A ¹ represents —R ¹ O—, — (R ² O) _s —, —CH ₂ CH (OH) CH ₂ O— or — (R ³ OOC—R ⁴ —COO—) _t R ³ O R ¹ is a divalent hydrocarbon group having 2 to 36 carbon atoms, R ² is an alkanediyl group having 2 to 4 carbon atoms, s is a number of 1 to 60 in terms of the average number of moles added, R ³ is a divalent hydrocarbon group having 2 to 18 carbon atoms or — (R ⁵ O) _u R ⁵ — (wherein R ⁵ is an alkanediyl group having 2 to 4 carbon atoms, u is 1 in terms of the average number of moles added. R ⁴ is a divalent hydrocarbon group having 2 to 18 carbon atoms, and t is an average value of 1 to 30. ]
And 0.3 to 7 parts by mass of a compound represented by formula (D)

Wherein, R ⁶ is a straight-chain or 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is independently a group capable of binding with two silicon _{atoms, [-0-] 0. 5, [} - 0-G-] 0.5 or with a group selected from [-O-G-O-] _0.5 Each of Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and each of Z ^c is independently —Cl , —Br, —OR ⁷ , R ⁷ C (═O) O—, R ⁷ R ⁸ C═NO—, R ⁷ R ⁸ N—, R ⁷ —, HO—G—O— G is in accordance with the above notation, and R ⁷ and R ⁸ are each independently a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms.
m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and (u / 2) + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a in the plurality of B parts Each of _u , Z ^b _v and Z ^c _w may be the same or different. ]
A rubber composition containing a silane coupling agent represented by the formula (B) in a proportion of 2 to 30% by mass with respect to the inorganic filler of the component (B),
[2] The component (D) represented by the general formula (II) is represented by the chemical formula (III),

Chemical formula (IV),

And chemical formula (V)

[Wherein, L is independently an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms, and x = m and y = n. ] The tire according to the above [1], which is at least one selected from silane coupling agents represented by
[3] The tire according to [1] or [2], wherein the inorganic filler is silica.
[4] The tire according to any one of [1] to [3], including (B) 40 to 90 parts by mass of an inorganic filler with respect to 100 parts by mass of the rubber component (A),
[5] The tire according to any one of [1] to [4], further including (E) carbon black at a ratio of 5 to 40 parts by mass with respect to 100 parts by mass of the (A) rubber component.
[6] The tire according to any one of [1] to [5] above, wherein the compound represented by the general formula (I) of the component (C) is polyethylene glycol dimaleate or polyethylene glycol difumarate, and [7] The tire according to any one of [1] to [6], wherein the rubber composition is used for a tread.
Is to provide.

  According to the present invention, in an inorganic filler compounding system, an excellent composition comprising a silane coupling agent comprising a protected mercaptosilane having a specific structure and a maleic acid or fumaric acid ester of a polyhydric alcohol is used. It is possible to provide a tire, particularly a pneumatic tire, that can achieve both rolling resistance and good dry handling stability.

The tire of the present invention comprises (A) at least one rubber component selected from natural rubber and diene synthetic rubber, (B) inorganic filler, (C) maleic acid or fumarate ester of polyhydric alcohol, and ( D) A rubber composition containing a silane coupling agent made of protected mercaptosilane is used.
In the rubber composition used for the tire of the present invention, natural rubber and / or diene synthetic rubber is used as the rubber component (A). Examples of the diene synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), halogenated butyl rubber, ethylene-propylene-diene terpolymer (EPDM). ), Acrylonitrile-butadiene copolymer (NBR), and mixtures thereof. Further, a part thereof may have a branched structure by using a polyfunctional modifier, for example, a modifier such as tin tetrachloride. As the rubber component (A), it is preferable to use a diene rubber (A-1) having a weight average molecular weight of 800,000 or more. By using a high molecular weight polymer, the total number of terminals of the polymer is reduced, and the loss coefficient (loss tangent) is further reduced.
In the present invention, as the rubber component (A), natural rubber may be used alone, or one or more of the diene synthetic rubbers may be used, or a combination of natural rubber and one or more diene synthetic rubbers may be used. May be used.

In the rubber composition according to the present invention, examples of the inorganic filler used as the component (B) include silica or an inorganic filler represented by the following general formula (VI).
jM ¹ · pSiOq · rH ₂ O (VI)
In the formula, M ¹ is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium, and zirconium, oxides or hydroxides of these metals, and hydrates thereof, or carbonates of these metals. And j, p, q and r are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. In the general formula (VI), when p and r are both 0, the inorganic compound is at least one metal selected from aluminum, magnesium, titanium, calcium and zirconium, metal oxide or metal hydroxide. It becomes a thing.

This inorganic filler of the component (B) is blended in the range of 20 to 150 parts by mass, preferably 40 to 90 parts by mass with respect to 100 parts by mass of the rubber component as the component (A). When the blending amount of the inorganic filler is less than 20 parts by mass, the effect of improving the reinforcing properties and other physical properties is insufficient, and when it exceeds 150 parts by mass, workability and rolling resistance are deteriorated.
The inorganic fillers such as silica and the inorganic filler represented by the general formula (VI) may be used alone or in combination of two or more.

As the inorganic filler (B), silica is preferable. Examples of silica include wet silica (hydrous silicic acid) and dry silica (anhydrous silicic acid). Among them, wet silica has the most remarkable effect of improving fracture characteristics and achieving both wet grip and low rolling resistance. Is preferred.
The wet silica preferably has a nitrogen adsorption specific surface area (N ₂ SA) according to the BET method of 140 to 280 m ² / g from the viewpoints of balance of reinforcement, workability, wet grip properties, and wear resistance, It is more preferable that it is 160-250 m < ² > / g. Suitable wet silica includes, for example, AQ, VN3, LP, NA, etc. manufactured by Tosoh Silica Co., Ltd. and Ultrazil VN3 (N ₂ SA: 175 m ² / g) manufactured by Degussa.

As the inorganic filler represented by the general formula (VI), .gamma.-alumina, alumina (Al ₂ O ₃₎ such as α- alumina, boehmite, alumina monohydrate such as diaspore (Al ₂ O ₃ · H ₂ O), Gibbsite, Bayerite, etc. Aluminum hydroxide [Al (OH) ₃ ], Aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], Magnesium hydroxide [Mg (OH) ₂ ], Magnesium oxide (MgO), Carbonic acid Magnesium (MgCO ₃ ), talc (3MgO · 4SiO ₂ · H ₂ O), attapulgite (5MgO · 8SiO ₂ · 9H ₂ O), titanium white (TiO ₂ ), titanium black (TiO _2n-1 ), calcium oxide (CaO ), calcium hydroxide [Ca (OH) _2], magnesium aluminum oxide _{(MgO · Al 2 O 3)} , clay _{(Al 2 O 3 · 2SiO 2} ), kaolin ( _{l 2 O 3 · 2SiO 2 ·} 2H 2 O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate (Al ₂ SiO ₅ , Al ₄ · 3SiO ₄ · 5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), calcium silicate (Ca ₂ · SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO (OH) ₂ · nH ₂ O], zirconium carbonate [ Zr (CO _{3) 2],} hydrogen to correct electric charge as various zeolites, crystalline aluminosilicates such as containing alkali metal or alkaline earth metal is used Kill. Further, it is preferable that M ¹ in the general formula (VI) is at least one selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate.

In the rubber composition according to the present invention, carbon black can be used in combination with the inorganic filler as the component (E) as necessary. The blending amount of the carbon black is preferably 5 to 40 parts by mass, and 5 to 30 parts by mass with respect to 100 parts by mass of the rubber component as the component (A) from the viewpoints of the reinforcing effect, workability, and other performance. More preferred. Examples of carbon black include FEF, GPF, SRF, HAF, N339, IISAF, ISAF, and SAF. Nitrogen adsorption specific surface area of the carbon black _{(N 2 SA, JIS K 6217-2} : conforms to 2001) is preferably from 20~160m ² / g, more preferably 70~160m ² / g. Further, preferably dibutyl phthalate oil absorption: a (DBP, JIS K 6217-4 compliant to 2001) of carbon black 80~170cm ³ / 100g. By using these carbon blacks, the effect of improving various physical properties, particularly fracture characteristics, is increased. Preferred carbon blacks are HAF, N339, IISAF, ISAF and SAF.

In the rubber composition according to the present invention, as the component (C), the general formula (I)
HOOC-CH = CH-COO- A 1 -OOC-CH = CH-COOH ··· (I)
In other words, a polyhydric alcohol maleic acid or fumaric acid ester is used.
In the general formula (I), A ¹ is —R ¹ O—, — (R ² O) _s —, —CH ₂ CH (OH) CH ₂ O— or — (R ³ OOC—R ⁴ —COO—) _t. It is a group represented by R ³ O—. Here, R ¹ represents a divalent hydrocarbon group having 2 to 36 carbon atoms. Examples of the divalent hydrocarbon group include an alkanediyl group or alkenediyl group having 2 to 36 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, preferably an alkane having 2 to 18 carbon atoms. A diyl group or a phenylene group, more preferably an alkanediyl group having 4 to 12 carbon atoms. R ² is an alkanediyl group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, and s is a number from 1 to 60 indicating the average number of moles added of the oxyalkanediyl group, preferably 2 to 40. More preferably, the number is 4 to 30. R ³ represents a divalent hydrocarbon group having 2 to 18 carbon atoms or — (R ⁵ O) _u R ⁵ —. Examples of the divalent hydrocarbon group include an alkanediyl group or alkenediyl group having 2 to 18 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. In — (R ⁵ O) _u R ⁵ —, R ⁵ is an alkanediyl group having 2 to 4 carbon atoms, u is a number of 1 to 30 indicating the average number of moles added of the oxyalkanediyl group, preferably 1 to 20, more preferably a number from 2 to 15. R ⁴ represents a divalent hydrocarbon group having 2 to 18 carbon atoms. Examples of the divalent hydrocarbon group include an alkanediyl group or alkenediyl group having 2 to 18 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, preferably an alkane having 2 to 12 carbon atoms. A diyl group or a phenylene group, more preferably an alkanediyl group having 2 to 8 carbon atoms. t is an average value of 1 to 30, preferably 1 to 20, and more preferably 1 to 15.

Specific examples of the compound represented by the general formula (I) include glycerol dimaleate, 1,4-butanediol dimaleate, 1,6-hexanediol dimaleate alkylene diol dimaleate, 1,6 -Difumarate of alkylene diol such as hexanediol difumarate, dimaleate of polyoxyalkylene glycol such as PEG200 dimaleate, PEG600 dimaleate (herein, PEG200 and PEG600 indicate polyethylene glycol having an average molecular weight of 200 or 600, respectively), both ends Polybutylene maleate having a carboxyl group at both ends, poly (PEG200) maleate having a carboxyl group at both ends, etc., both end carboxylate type polyalkylene glycol / maleic polyester, carboxyl at both ends Carboxylic acid types such as polybutylene adipate maleate having polyoxyalkylene glycol, polyoxyalkylene glycol difumarate such as PEG600 difumarate, polybutylene fumarate having carboxyl groups at both ends, poly (PEG200) fumarate having carboxyl groups at both ends Examples include polyalkylene glycol / fumaric acid polyester.
Among these, polyethylene glycol dimaleate or polyethylene glycol difumarate is preferable in terms of performance and economy.
The molecular weight of the component (C) is preferably 250 or more, more preferably in the range of 250 to 5000, and particularly preferably in the range of 250 to 3000. Within this range, the flash point is high, which is desirable not only from the viewpoint of safety, but also from the viewpoint of the working environment because it produces less smoke.

In the rubber composition according to the present invention, the component (C) can form a chemical bond through an inorganic filler, particularly silica and a hydrogen bond, and a polymer and sulfur. The rate (E ′) can be increased, thereby improving the dry handling stability of the tire of the present invention.
In this invention, the said (C) component may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the compounding quantity is selected in the range of 0.3-7 mass parts with respect to 100 mass parts of rubber components which are (A) components. If the blending amount of the component (C) is in the above range, the resulting tire of the present invention can maintain rolling resistance performance and improve dry handling stability. The preferable compounding quantity of the said (C) component is 0.5-5 mass parts.

  In the rubber composition according to the present invention, as the component (D), the general formula (II)

A silane coupling agent comprising a protected mercaptosilane represented by the formula:
In the general formula (II), R ⁶ is a linear or branched alkyl group having 1 to 20 carbon atoms, and G is independently an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms. There, a group Z ^a is capable of independently binding to two silicon _{atoms, [-0-] 0. 5, [} - 0-G-] 0.5 and [-O-G-O-] _0.5 Z ^b is a group that can be independently bonded to two silicon atoms, is a functional group represented by [—O—G—O—] _0.5 , and Z ^c is Independently —Cl, —Br, —OR ⁷ , R ⁷ C (═O) O—, R ⁷ R ⁸ C═NO—, R ⁷ R ⁸ N—, R ⁷ —, HO—G—O— G is the same as the above-mentioned notation, and R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 20 carbon atoms.
m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and (u / 2) + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different, and when there are a plurality of B parts, Z ^a in the plurality of B parts Each of _u , Z ^b _v and Z ^c _w may be the same or different.

The rubber composition according to the present invention can provide a pneumatic tire having improved rolling resistance performance by using such a silane coupling agent as the component (D).
In the present invention, the silane coupling agent of component (D) may be used alone or in combination of two or more. Moreover, the compounding quantity is selected in 2-30 mass% with respect to the inorganic filler of the said (B) component. If the blending amount of the silane coupling agent is within the above range, the effects of the present invention are sufficiently exhibited. A preferable blending amount is in the range of 5 to 26% by mass.

  As the silane coupling agent obtained by the general formula (II), the following chemical formula (III), chemical formula (IV), and chemical formula (V),

［式中Ｌはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基であり、ｘ＝ｍ、ｙ＝ｎである。］を挙げることができる。

[In the formula, each L is independently an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms, and x = m and y = n. ] Can be mentioned.

As the silane coupling agent represented by the chemical formula (III), a product name “NXT Low-V Silane (trademark)” manufactured by Momentive Performance Materials is commercially available.
Further, as the silane coupling agent represented by the chemical formula (IV), a product name “NXT Ultra Low-V Silane (trademark)” manufactured by Momentive Performance Materials is also available as a commercial product.
Furthermore, examples of the silane coupling agent represented by the chemical formula (V) include a product name “NXT _- Z (trademark)” manufactured by Momentive Performance Materials.

  At least one selected from the silane coupling agents represented by the chemical formulas (III), (IV) and (V) (hereinafter referred to as “NXT silane”) has a weight average molecular weight of 800,000 or more. By using together with a certain diene rubber (A-1), the loss factor (tan δ) can be greatly reduced. This is because the use of NXT silane can improve the dispersion of the inorganic filler, and the loss factor is reduced in synergy with the loss factor reduction effect of the high molecular weight polymer. Thereby, rolling resistance performance will improve significantly by using the above two.

In addition, the silane coupling agent represented by the chemical formula (V) {particularly the trade name “NXT _- Z (trademark)”} has a large number of alkoxysilane carbon atoms, that is, a small number of ethoxy groups. (Especially alcohol) is less generated and environmental load is small, which is preferable. The silane coupling agent represented by the chemical formula (V) {particularly the trade name “NXT _- Z (trademark)”} has excellent low heat buildup as a tire performance, greatly improves rolling resistance performance and wear resistance. Further, it is more preferable to obtain a rubber composition that also improves.
Further, by combining the silane coupling agent represented by the chemical formula (V) and the component (C), the effect of dispersing the inorganic filler (particularly silica) of the silane coupling agent represented by the chemical formula (V). Can suppress an increase in hysteresis loss due to the component (C), effectively and superior to the case where each of the silane coupling agent represented by the chemical formula (V) and the component (C) is used alone. It can achieve both rolling resistance and good dry handling stability.

  Furthermore, in order to couple the silane coupling agent of component (D) and the polymer, it is preferable to mix a proton donor typified by DPG (diphenylguanidine) or the like in the final kneading step as a deprotecting agent. The amount used is preferably from 0.1 to 5.0 parts by weight, more preferably from 0.2 to 3.0 parts by weight, per 100 parts by weight of the rubber component.

In the rubber composition according to the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an anti-aging agent, as long as the object of the present invention is not impaired. , Scorch inhibitor, zinc white, stearic acid and the like can be contained.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of rubber components, 0.3-5.0 mass parts Is more preferable, and 0.5 to 5.0 parts by mass is even more preferable.

  The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.

  Examples of the process oil that can be used in the rubber composition according to the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it is 100 parts by mass or less, the tensile strength and low heat build-up of the vulcanized rubber will be good.

The rubber composition according to the present invention is obtained by kneading using a kneading machine such as a Banbury mixer, roll, internal mixer, etc., vulcanized after molding, and used as a tire tread as a tire application. It is done. In addition, it can also be used for under treads, sidewalls, carcass coating rubber, belt coating rubber, bead filler, chafer, bead coating rubber and the like.
The tire of the present invention is produced by a usual method using the rubber composition according to the present invention. That is, if necessary, the rubber composition containing various chemicals as described above is processed into a tire member, preferably a tire tread, at an unvulcanized stage, and is applied by a usual method on a tire molding machine. Molded and green tires are molded. The green tire is heated and pressed in a vulcanizer to obtain a tire.
The tire of the present invention thus obtained, particularly a pneumatic tire, retains excellent rolling resistance performance and has good dry handling stability.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.
In addition, the rolling resistance performance and the dry steering stability of the test tires obtained in each example were evaluated according to the following methods.
(1) Rolling resistance performance Under the conditions of an internal pressure of 0.2 MPa, a load of 4315 N, and a rim 7JJ, the test tire was brought into contact with a drum having an outer diameter of 1.7 m, the drum was rotated, and the speed was increased to 120 km / hr. From the value calculated from the moment of inertia when the drum was coasted and the speed was 80 km / hour, the following equation was used. The numerical value is expressed as an index with Comparative Example 1 being 100, and it is preferably as large as possible.
Index value = [(the moment of inertia of the tire of Comparative Example 1) / (the moment of inertia of the test tire)] × 100
(2) Dry handling stability All four passenger cars with a displacement of 2000 cc are fitted with test tires using the same rubber composition, the dry road surface braking distance on the test course is obtained, and the reciprocal of the braking distance of Comparative Example 1 is obtained. The index was expressed as 100 by the following formula. The larger the index value, the better the dry handling stability.
Index value = [(braking distance of tire of comparative example 1) / (braking distance of test tire)] × 100

Examples 1-7 and Comparative Examples 1-7
Fourteen types of rubber compositions having the composition shown in Table 1 were prepared, and 14 types of pneumatic tires having a tire size of 215 / 45R17 were prepared according to a conventional method.
Each tire was evaluated for rolling resistance performance and dry handling stability. The results are shown in Table 1.

［注］
１）ＪＳＲ（株）製、商品名「ＳＢＲ０１２０（商標）」、オイル含量２７．３質量％油展ＳＢＲ
２）Ｎ１３４、東海カーボン（株）製、商品名「シースト９Ｈ（商標）」、窒素吸着比表面積（Ｎ₂ＳＡ：１４６ｍ²／ｇ）
３）東ソー・シリカ（株）製、商品名「ニプシルＡＱ（商標）」
４）両末端カルボン酸型の平均重合度４．５のポリエチレングリコール／マレイン酸ポリエステル（ポリエステル部分の重合度５）
５）ビス（３−トリエトキシシリルプロピル）テトラスルフィド、デグサ社製シランカップリング剤、商品名「Ｓｉ６９（商標）」
６）Ｍｏｍｅｎｔｉｖｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ社製、商品名「ＮＸＴ_-Ｚ（商標）」
７）Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン、大内新興化学工業（株）製、商品名「ノクラック８１０−ＮＡ（商標）」
８）脱保護化剤：ジフェニルグアニジン（ＤＰＧ）、大内新興化学工業（株）製、商品名「ノクセラーＤ（商標）」
９）ジベンゾチアジルジスルフィド、大内新興化学工業（株）製、商品名「ノクセラーＤＭ（商標）」
１０）Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド、大内新興化学工業（株）製、商品名「ノクセラーＣＺ（商標）」

[note]
1) Product name “SBR0120 (trademark)” manufactured by JSR Corporation, oil content 27.3 mass% oil-extended SBR
2) N134, manufactured by Tokai Carbon Co., Ltd., trade name “SEAST 9H (trademark)”, nitrogen adsorption specific surface area (N ₂ SA: 146 m ² / g)
3) Product name “Nipsil AQ ™” manufactured by Tosoh Silica Co., Ltd.
4) Polyethylene glycol / maleic polyester having an average degree of polymerization of 4.5 at both terminal carboxylic acid types (polymerization degree of polyester part 5)
5) Bis (3-triethoxysilylpropyl) tetrasulfide, a silane coupling agent manufactured by Degussa, trade name “Si69 (trademark)”
6) Product name “NXT _- Z (trademark)” manufactured by Momentive Performance Materials
7) N-isopropyl-N′-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 810-NA (trademark)”
8) Deprotecting agent: Diphenylguanidine (DPG), manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller D (trademark)”
9) Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller DM ™”
10) N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller CZ (trademark)”

From Table 1, it can be seen that:
The pneumatic tires of Examples 1 to 7 are both excellent in rolling resistance performance and dry steering stability. On the other hand, any of the pneumatic tires of Comparative Examples 1 to 7 has low rolling resistance performance and dry steering stability.

  Since the tire of the present invention can achieve both excellent rolling resistance and good dry handling stability, various pneumatic tires, for example, pneumatic tires for passenger cars, pneumatic tires for light vehicles, and pneumatic trucks for light trucks. It is suitably used as a tire, a pneumatic tire for trucks and buses, etc.

Claims (7)

(A) At least one rubber component selected from natural rubber and diene-based synthetic rubber, and 100 parts by mass thereof, (B) 20 to 150 parts by mass of inorganic filler and (C) general formula (I)
HOOC-CH = CH-COO- A 1 -OOC-CH = CH-COOH ··· (I)
[Wherein, A ¹ represents —R ¹ O—, — (R ² O) _s —, —CH ₂ CH (OH) CH ₂ O— or — (R ³ OOC—R ⁴ —COO—) _t R ³ O R ¹ is a divalent hydrocarbon group having 2 to 36 carbon atoms, R ² is an alkanediyl group having 2 to 4 carbon atoms, s is a number of 1 to 60 in terms of the average number of moles added, R ³ is a divalent hydrocarbon group having 2 to 18 carbon atoms or — (R ⁵ O) _u R ⁵ — (wherein R ⁵ is an alkanediyl group having 2 to 4 carbon atoms, u is 1 in terms of the average number of moles added. R ⁴ is a divalent hydrocarbon group having 2 to 18 carbon atoms, and t is an average value of 1 to 30. ]
And 0.3 to 7 parts by mass of a compound represented by formula (D)

Wherein, R ⁶ is a straight-chain or 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is Each independently a group capable of bonding to two silicon atoms, a group selected from [-0-] _0.5 , [-0-G-] _0.5 or [-O-G-O-] _0.5 ; Z ^b is a group that can independently bond to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 , and Z ^c is independently —Cl, — It is a functional group represented by Br, —OR ⁷ , R ⁷ C (═O) O—, R ⁷ R ⁸ C═NO—, R ⁷ R ⁸ N—, R ⁷ —, HO—G—O—. , G is identical to the above notation, and R ⁷ and R ⁸ are each independently a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms.
m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and (u / 2) + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a in the plurality of B parts Each of _u , Z ^b _v and Z ^c _w may be the same or different. ]
A tire comprising a rubber composition containing a silane coupling agent represented by the formula (B) in a proportion of 2 to 30% by mass relative to the inorganic filler of the component (B). The component (D) represented by the general formula (II) is represented by the chemical formula (III),

Chemical formula (IV),

And chemical formula (V)

[Wherein, L is independently an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms, and x = m and y = n. The tire according to claim 1, which is at least one selected from silane coupling agents represented by the formula:   The tire according to claim 1 or 2, wherein the inorganic filler is silica.   The tire according to any one of claims 1 to 3, comprising (B) 40 to 90 parts by mass of an inorganic filler with respect to 100 parts by mass of the rubber component (A).   Furthermore, the tire in any one of Claims 1-4 which contain (E) carbon black in the ratio of 5-40 mass parts with respect to 100 mass parts of (A) rubber components.   The tire according to any one of claims 1 to 5, wherein the compound represented by the general formula (I) of component (C) is polyethylene glycol dimaleate or polyethylene glycol difumarate.   The tire according to any one of claims 1 to 6, wherein the rubber composition is used for a tread.