JP2011178958A - Rubber composition for chafer and pneumatic tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition for a chafer improving low heat buildup (low fuel consumption) and rubber strength (tear strength) with good balance and a pneumatic tire using the same. <P>SOLUTION: The rubber composition for a chafer contains a rubber component containing butadiene rubber modified with a compound represented by a specific formula, silica, and a silane coupling agent represented by a specific formula and/or a silane coupling agent comprising a bonding unit A represented by a specific formula and a bonding unit B represented by a specific formula. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a rubber composition for chafers and a pneumatic tire using the same.

Conventionally, in consideration of environmental problems and economics, reducing the rolling resistance of a tire (improving rolling resistance performance) has led to a reduction in fuel consumption of the vehicle. In recent years, the demand for lower fuel consumption of vehicles has become stronger, and not only rubber compositions for producing treads with high occupancy ratio in tires among tire components, but also for example for chafer rubber However, excellent low heat generation is required.

As a method of satisfying the low heat build-up in the chafer rubber, a method of reducing the content of reinforcing fillers such as silica and carbon black is known. However, in this case, the reinforcing property is lowered, and the rubber strength (tear strength) is lowered. Therefore, when the tire is mounted on the rim or removed from the rim, damage may occur at a contact portion (chafer portion) with the rim. If the chafer part is damaged, air leakage or the like may occur, which may cause a problem in tire safety. Thus, it is desired to provide a chafer rubber excellent in balance between low heat generation (low fuel consumption) and rubber strength (tear strength).

Patent Document 1 discloses a rubber composition that can improve processability, workability, and fuel efficiency by blending a silane coupling agent having a mercapto group. However, there is room for improvement in the balance between low heat generation (low fuel consumption) and rubber strength (tear strength). In addition, application of the rubber composition to chafer rubber has not been studied.

JP 2009-126907 A

This invention solves the said subject, and provides the rubber composition for chafers which can improve low exothermic property (low fuel consumption property) and rubber strength (tear strength) in good balance, and a pneumatic tire using the same. Objective.

（式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、同一若しくは異なって、分岐若しくは非分岐のアルキル基、分岐若しくは非分岐のアルコキシ基、分岐若しくは非分岐のシリルオキシ基、分岐若しくは非分岐のアセタール基、カルボキシル基、メルカプト基又はこれらの誘導体を表す。Ｒ^４及びＲ^５は、同一若しくは異なって、水素原子又は分岐若しくは非分岐のアルキル基を表す。ｎは整数を表す。）

（式（２）中、Ｒ^６は−Ｏ−（Ｒ^１０−Ｏ）_ｍ−Ｒ^１１（ｍ個のＲ^１０は、同一又は異なって、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。Ｒ^１１は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基又は炭素数７〜３０のアラルキル基を表す。ｍは１〜３０の整数を表す。）で表される基を表す。Ｒ^７及びＲ^８は、同一若しくは異なって、Ｒ^６と同一の基、分岐若しくは非分岐の炭素数１〜１２のアルキル基又は−Ｏ−Ｒ^１２（Ｒ^１２は水素原子、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基又は炭素数７〜３０のアラルキル基を表す。）で表される基を表す。Ｒ^９は、分岐若しくは非分岐の炭素数１〜３０のアルキレン基を表す。）

（式（３）、（４）中、ｘは０以上の整数である。ｙは１以上の整数である。Ｒ^１３は水素、ハロゲン、分岐若しくは非分岐の炭素数１〜３０のアルキル基若しくはアルキレン基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基若しくはアルケニレン基、分岐若しくは非分岐の炭素数２〜３０のアルキニル基若しくはアルキニレン基、又は該アルキル基若しくは該アルケニル基の末端が水酸基若しくはカルボキシル基で置換されたものを示す。Ｒ^１４は水素、分岐若しくは非分岐の炭素数１〜３０のアルキレン基若しくはアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニレン基若しくはアルケニル基、又は分岐若しくは非分岐の炭素数２〜３０のアルキニレン基若しくはアルキニル基を示す。Ｒ^１３とＲ^１４とで環構造を形成してもよい。） The present invention provides a rubber component containing a butadiene rubber modified with a compound represented by the following formula (1), silica, a silane coupling agent represented by the following formula (2) and / or the following formula (3). And a silane coupling agent comprising a binding unit B represented by the following formula (4).

(In formula (1), R ¹ , R ² and R ³ are the same or different and are branched or unbranched alkyl groups, branched or unbranched alkoxy groups, branched or unbranched silyloxy groups, branched or unbranched. R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a branched or unbranched alkyl group, and n represents an integer.

(In Formula (2), R ⁶ is —O— (R ¹⁰ —O) _m —R ¹¹ (m R ^{10 s} are the same or different and are branched or unbranched C 1-30 divalent divalent) R ¹¹ represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms. Represents an aralkyl group of ˜30. M represents an integer of 1 to 30.) R ⁷ and R ⁸ are the same or different and are the same group as R ⁶ , branched or unbranched. An alkyl group having 1 to 12 carbon atoms or —O—R ¹² (R ¹² is a hydrogen atom, a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, C6-C30 aryl group or C7-C30 aralkyl .R ⁹ represents a group represented by a group.) Represents a branched or unbranched alkylene group having 1 to 30 carbon atoms.)

(In the formulas (3) and (4), x is an integer of 0 or more. Y is an integer of 1 or more. R ¹³ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, or An alkylene group, a branched or unbranched alkenyl group or alkenylene group having 2 to 30 carbon atoms, a branched or unbranched alkynyl group or alkynylene group having 2 to 30 carbon atoms, or a terminal of the alkyl group or alkenyl group is a hydroxyl group or R ¹⁴ represents one substituted with a carboxyl group, R ¹⁴ represents hydrogen, branched or unbranched alkylene group or alkyl group having 1 to 30 carbon atoms, branched or unbranched C 2-30 alkenylene group or alkenyl group, or A branched or unbranched alkynylene or alkynyl group having 2 to 30 carbon atoms, wherein R ¹³ and R ¹⁴ are ring structures; May be formed.)

（式（５）中、ｚは１〜８の整数を表す。） The chafer rubber composition preferably contains a vulcanization accelerator represented by the following formula (5).

(In formula (5), z represents an integer of 1 to 8.)

In the chafer rubber composition, the content of butadiene rubber modified with the compound represented by the above formula (1) in 100% by mass of the rubber component is preferably 20% by mass or more.

The present invention also relates to a pneumatic tire having a chafer manufactured using the rubber composition.

According to this invention, the rubber component containing the butadiene rubber modified with the compound represented by the above formula (1), silica, the silane coupling agent represented by the above formula (2) and / or the above formula ( Since it is a rubber composition for chafers comprising a bonding unit A represented by 3) and a silane coupling agent comprising the coupling unit B represented by the above formula (4), low heat build-up (low fuel consumption), rubber strength (Tear strength) can be improved in a well-balanced manner, and by using the rubber composition as a tire chafer, a pneumatic tire with a low balance of low heat buildup (low fuel consumption) and rubber strength (tear strength) is provided. can do.

The chafer rubber composition of the present invention comprises a rubber component containing a butadiene rubber modified with a compound represented by the above formula (1), silica, a silane coupling agent represented by the above formula (2), and And / or a silane coupling agent comprising a binding unit A represented by the above formula (3) and a binding unit B represented by the above formula (4).

In this invention, the butadiene rubber (modified butadiene rubber) by which the terminal was modified | denatured with the compound represented by following formula (1) is included as a rubber component. By including the modified butadiene rubber, the modifying group is bonded to silica, energy loss due to rubber movement can be reduced, and low heat buildup (low fuel consumption) can be improved.

R ¹ , R ² and R ³ in the above formula (1) are the same or different and each represents a branched or unbranched alkyl group, a branched or unbranched alkoxy group, a branched or unbranched silyloxy group, a branched or unbranched group. An acetal group, a carboxyl group (—COOH), a mercapto group (—SH) or a derivative thereof is represented. Examples of the branched or unbranched alkyl group include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and t-butyl group. . Examples of the branched or unbranched alkoxy group include an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group (preferably C1-C6, More preferably, C1-C4) etc. are mentioned. The alkoxy group includes a cycloalkoxy group (cycloalkoxy group having 5 to 8 carbon atoms such as cyclohexyloxy group) and an aryloxy group (aryloxy group having 6 to 8 carbon atoms such as phenoxy group and benzyloxy group). ) Is also included.

Examples of the branched or unbranched silyloxy group include a silyloxy group substituted with an aliphatic group having 1 to 20 carbon atoms and an aromatic group (trimethylsilyloxy group, triethylsilyloxy group, triisopropylsilyloxy group, diethylisopropylsilyl group). Oxy group, t-butyldimethylsilyloxy group, t-butyldiphenylsilyloxy group, tribenzylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, and the like.

Examples of the branched or unbranched acetal group include groups represented by -C (RR ')-OR "and -O-C (RR')-OR". Examples of the former include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, an isopropoxymethyl group, a t-butoxymethyl group, and a neopentyloxymethyl group. The latter includes a methoxymethoxy group, an ethoxy group, and the like. Methoxy group, propoxymethoxy group, i-propoxymethoxy group, n-butoxymethoxy group, t-butoxymethoxy group, n-pentyloxymethoxy group, n-hexyloxymethoxy group, cyclopentyloxymethoxy group, cyclohexyloxymethoxy group, etc. Can be mentioned. R ¹ , R ² and R ³ are preferably alkoxy groups. Thereby, the outstanding low exothermic property (low fuel consumption) can be obtained.

Examples of the branched or unbranched alkyl group of R ⁴ and R ^{5 in} the formula (1) include the same groups as the branched or unbranched alkyl group.

As n (integer) of said Formula (1), 1-5 are preferable. Thereby, the outstanding low exothermic property (low fuel consumption) can be obtained. Furthermore, n is more preferably 2 to 4, and most preferably 3. When n is 0, it is difficult to bond a silicon atom and a nitrogen atom, and when n is 6 or more, the effect as a modifier is reduced.

Specific examples of the compound represented by the above formula (1) include 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, Aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropylmethyldibutoxysilane, dimethylaminomethyltrimethoxysilane, 2-dimethyl Aminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 4-dimethylaminobutyltrimethoxysilane, dimethylaminomethyldimethoxymethylsilane, 2-dimethylaminoethyldimethoxy Methylsilane, 3-dimethylaminopropyldimethoxymethylsilane, 4-dimethylaminobutyldimethoxymethylsilane, dimethylaminomethyltriethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 4-dimethylaminobutyl Triethoxysilane, dimethylaminomethyldiethoxymethylsilane, 2-dimethylaminoethyldiethoxymethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 4-dimethylaminobutyldiethoxymethylsilane, diethylaminomethyltrimethoxysilane, 2- Diethylaminoethyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, 4-diethylaminobutyltrimethoxysilane, diethylamino Tildimethoxymethylsilane, 2-diethylaminoethyldimethoxymethylsilane, 3-diethylaminopropyldimethoxymethylsilane, 4-diethylaminobutyldimethoxymethylsilane, diethylaminomethyltriethoxysilane, 2-diethylaminoethyltriethoxysilane, 3-diethylaminopropyltriethoxysilane 4-diethylaminobutyltriethoxysilane, diethylaminomethyldiethoxymethylsilane, 2-diethylaminoethyldiethoxymethylsilane, 3-diethylaminopropyldiethoxymethylsilane, 4-diethylaminobutyldiethoxymethylsilane, and the like. These may be used alone or in combination of two or more.

The vinyl content of the modified butadiene rubber is preferably 35% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. When the vinyl content exceeds 35% by mass, the low exothermic property tends to be impaired. The lower limit of the vinyl content is not particularly limited.
The vinyl content (1,2-bond butadiene unit amount) can be measured by infrared absorption spectrum analysis.

Examples of the modification method of butadiene rubber with the compound (modifier) represented by the above formula (1) include conventionally known methods such as methods described in JP-B-6-53768 and JP-B-6-57767. Techniques can be used. For example, the butadiene rubber may be brought into contact with the modifying agent, the butadiene rubber is polymerized, and a predetermined amount of the modifying agent is added to the polymer rubber solution, and the modifying agent is added to the butadiene rubber solution and reacted. Methods and the like.

The content of the modified butadiene rubber in 100% by mass of the rubber component is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. If it is less than 20% by mass, low heat build-up (low fuel consumption) may be impaired. The content of the modified butadiene rubber is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. When it exceeds 80 mass%, workability may be deteriorated.

The rubber component that can be used in the present invention other than the modified butadiene rubber is not particularly limited, and natural rubber (NR), epoxidized natural rubber (ENR), isoprene rubber (IR), butadiene rubber (BR), and styrene butadiene. Examples include diene rubbers such as rubber (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and diene synthetic rubbers such as butyl rubber (IIR). Diene rubbers may be used alone or in combination of two or more. Among these, NR and BR are preferable because low exothermic properties (low fuel consumption) and durability (rubber strength (tear strength)) can be obtained in a well-balanced manner.

The NR is not particularly limited, and for example, SIR20, RSS # 3, TSR20, deproteinized natural rubber (DPNR), high-purity natural rubber (HPNR), etc., which are common in the tire industry can be used.

The content of NR in 100% by mass of the rubber component is preferably 20% by mass or more, more preferably 30% by mass or more. If it is less than 20% by mass, for example, the content of BR is relatively increased, and the workability tends to deteriorate. The NR content is preferably 80% by mass or less, more preferably 75% by mass or less. When it exceeds 80% by mass, for example, the BR content is relatively reduced, and the low heat build-up tends to be impaired.

In the present invention, silica is used. By blending silica with the modified butadiene rubber, good low heat build-up (low fuel consumption) and high rubber strength (tear strength) can be obtained. The silica is not particularly limited, and examples thereof include dry process silica (anhydrous silicic acid), wet process silica (hydrous silicic acid), and the like, but wet process silica is preferable because of its large number of silanol groups.

The nitrogen adsorption specific surface area _(N 2 SA) of silica is preferably not less than ^{40 m} 2 / g, more preferably at least ^{50 m} 2 / g, more preferably not less than ^{80m 2 / g, 100m 2 /} g or more is particularly preferable. If it is less than 40 m < ² > / g, there exists a tendency for the fracture strength after vulcanization to fall. The _N 2 SA of the silica is preferably 250 meters ² / g or less, more preferably 200 meters ² / g, more preferably not more than 150m ² / g. When it exceeds 250 m ² / g, there is a tendency that low heat build-up and rubber processability are lowered.
The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

The content of silica is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and still more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. When the amount is less than 20 parts by mass, there is a tendency that a sufficient effect due to silica blending cannot be obtained. The content of the silica is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 80 parts by mass or less. When the amount exceeds 150 parts by mass, it is difficult to disperse silica in rubber, and the processability of rubber tends to deteriorate.

In the present invention, a silane coupling agent comprising a silane coupling agent represented by the following formula (2) and / or a binding unit A represented by the following formula (3) and a binding unit B represented by the following formula (4) ( The bond unit B is an essential unit, and the bond unit A is an arbitrary unit.

By blending a silane coupling agent represented by the following formula (2), the balance between low heat build-up (low fuel consumption) and rubber strength (tear strength) is improved.

R ^{6 in the} above formula (2) is —O— (R ¹⁰ —O) _m —R ¹¹ (m R ^10s are the same or different and are branched or unbranched divalent carbon atoms having 1 to 30 carbon atoms. R ¹¹ represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 to 7 carbon atoms. Represents an aralkyl group of 30. m represents an integer of 1 to 30).

R ¹⁰ is the same or different and represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms).
Examples of the hydrocarbon group include a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, and a branched or unbranched alkynylene group having 2 to 30 carbon atoms. And an arylene group having 6 to 30 carbon atoms. Among these, the alkylene group is preferable because it is easily bonded to silica and is advantageous for low heat buildup (low fuel consumption).

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms) of R ¹⁰ include, for example, a methylene group, an ethylene group, a propylene group, and a butylene group. Pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.

The alkenylene group branched or unbranched carbon atoms 2 to 30 R ¹⁰ (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), for example, vinylene group, propenylene group, 2-propenylene Group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like.

Examples of the branched or unbranched alkynylene group having 2 to 30 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) for R ¹⁰ include, for example, an ethynylene group, a propynylene group, a butynylene group, and a pentynylene group. Hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, dodecynylene group and the like.

Examples of the arylene group having 6 to 30 carbon atoms (preferably 6 to 12 carbon atoms) of R ¹⁰ include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.

The m represents an integer of 1 to 30 (preferably 2 to 15, more preferably 3 to 7, further preferably 5 to 6). When m is 0, it is disadvantageous for bonding with silica, and when m is 31 or more, the reactivity with silica tends to decrease, and there is a possibility that sufficient low heat generation (low fuel consumption) cannot be obtained. is there.

R ¹¹ represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. To express. Among them, a branched or unbranched alkyl group having 1 to 30 carbon atoms is preferable because of its high reactivity with silica.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) of R ¹¹ include, for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 3 to 20 carbon atoms, more preferably 10 to 15 carbon atoms) for R ¹¹ include, for example, a vinyl group, a 1-propenyl group, and 2-propenyl. Group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group Group, pentadecenyl group, octadecenyl group and the like.

Examples of the aryl group having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R ¹¹ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms (preferably 7 to 20 carbon atoms) of R ¹¹ include a benzyl group and a phenethyl group.

Specific examples of R ^{6 in} the above formula (2) include, for example, —O— (C ₂ H ₄ —O) ₅ —C ₁₁ H ₂₃ , —O— (C ₂ H ₄ —O) ₅ —C ₁₂ H. _{25, -O- (C 2 H 4} -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 -C 14 H 29, -O- (C 2 H 4 -O) 5 _{-C 15 H 31, -O- (C} 2 H 4 -O) 3 -C 13 H 27, -O- (C 2 H 4 -O) 4 -C 13 H 27, -O- (C 2 H 4 _{-O) 6 -C 13 H 27,} -O- (C 2 H 4 -O) 7 -C 13 H 27 and the like. Among _{these, -O- (C 2 H 4 -O} ) 5 -C 11 H 23, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) _{5 -C 15 H 31, -O- (} C 2 H 4 -O) 6 -C 13 H 27 are preferable.

R ⁷ and R ⁸ are the same or different and are the same group as R ⁶ (that is, a group represented by —O— (R ¹⁰ —O) _m —R ¹¹ ), branched or unbranched carbon number 1 to 12 alkyl groups or —O—R ¹² (R ¹² is a hydrogen atom, a branched or unbranched C 1-30 alkyl group, a branched or unbranched C 2-30 alkenyl group, a C 6-30 carbon atom; An aryl group or an aralkyl group having 7 to 30 carbon atoms). Among them, because of its high reactivity with silica, it is represented by the same group as R ⁶ , —O—R ¹² (when R ¹² is a branched or unbranched C 1-30 alkyl group). Groups are preferred.

Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms) of R ⁷ and R ⁸ include, for example, methyl group, ethyl group, n- Examples include propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, and nonyl group. It is done.

Branched or unbranched having 1 to 30 carbon atoms of R ¹² as alkyl groups (preferably having 1 to 15 carbon atoms, more preferably 1 to 3 carbon atoms), for example, the number of carbon atoms of branched or unbranched the ^{R 11} The group similar to the alkyl group of 1-30 can be mentioned.

Branched or unbranched carbon atoms 2 to 30 R ¹² The alkenyl group (preferably having from 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms), for example, the number of carbon atoms of branched or unbranched the ^{R 11} The group similar to a 2-30 alkenyl group can be mentioned.

Examples of the aryl group having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R ¹² include the same groups as the aryl group having 6 to 30 carbon atoms of R ¹¹ .

Examples of the aralkyl group having 7 to 30 carbon atoms (preferably 7 to 15 carbon atoms) of R ¹² include the same groups as the aralkyl group having 7 to 30 carbon atoms of R ¹¹ .

Specific examples of R ⁷ and R ^{8 in} the above formula (2) include, for example, —O— (C ₂ H ₄ —O) ₅ —C ₁₁ H ₂₃ , —O— (C ₂ H ₄ —O) ₅ —. _{C 12 H 25, -O- (C} 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 -C 14 H 29, -O- (C 2 H 4 - _{O) 5 -C 15 H 31,} -O- (C 2 H 4 -O) 3 -C 13 H 27, -O- (C 2 H 4 -O) 4 -C 13 H 27, -O- (C _{2 H 4 -O) 6 -C 13} H 27, -O- (C 2 H 4 -O) 7 -C 13 H 27, C 2 H 5 -O-, CH 3 -O-, C 3 H 7 - O- etc. are mentioned. Among _{these, -O- (C 2 H 4 -O} ) 5 -C 11 H 23, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) _{5 -C 15 H 31, -O- (} C 2 H 4 -O) 6 -C 13 H 27, C 2 H 5 -O- are preferable.

Branched or unbranched having 1 to 30 carbon atoms of R ⁹ as the alkylene group (preferably having from 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), for example, the number of carbon atoms of branched or unbranched the ^{R 10} The same group as the alkylene group of 1-30 can be mentioned.

As the silane coupling agent represented by the above formula (2), for example, Si363 manufactured by Evonik Degussa can be used. These may be used alone or in combination of two or more.

By blending a silane coupling agent consisting of a binding unit B represented by the following formula (4) and a coupling unit A represented by the following formula (3) as necessary, bis (3-triethoxysilylpropyl) tetra Compared to conventional silane coupling agents such as sulfide, the balance between low heat build-up (low fuel consumption) and rubber strength (tear strength) can be improved.

The silane coupling agent composed of the binding unit A and the binding unit B is preferably a copolymer obtained by copolymerizing the binding unit B at a ratio of 1 to 70 mol% with respect to the total amount of the binding unit A and the binding unit B.

When the molar ratio of the bond unit A and the bond unit B satisfies the above conditions, an increase in viscosity during processing is suppressed as compared with polysulfide silanes such as bis- (3-triethoxysilylpropyl) tetrasulfide. This is presumably because the increase in Mooney viscosity is small because the sulfide portion of the bond unit A is a C—S—C bond and is thermally stable compared to tetrasulfide and disulfide.

Moreover, when the molar ratio of the bond unit A and the bond unit B satisfies the above conditions, shortening of the scorch time is suppressed as compared with mercaptosilane such as 3-mercaptopropyltrimethoxysilane. This is because the bond unit B has a structure of mercaptosilane, but the —C ₇ H ₁₅ portion of the bond unit A covers the —SH group of the bond unit B, so that it does not easily react with the polymer and scorch is less likely to occur. Conceivable.

（式（３）、（４）中、ｘは０以上の整数である。ｙは１以上の整数である。Ｒ^１３は水素、ハロゲン、分岐若しくは非分岐の炭素数１〜３０のアルキル基若しくはアルキレン基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基若しくはアルケニレン基、分岐若しくは非分岐の炭素数２〜３０のアルキニル基若しくはアルキニレン基、又は該アルキル基若しくは該アルケニル基の末端が水酸基若しくはカルボキシル基で置換されたものを示す。Ｒ^１４は水素、分岐若しくは非分岐の炭素数１〜３０のアルキレン基若しくはアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニレン基若しくはアルケニル基、又は分岐若しくは非分岐の炭素数２〜３０のアルキニレン基若しくはアルキニル基を示す。Ｒ^１３とＲ^１４とで環構造を形成してもよい。）

(In the formulas (3) and (4), x is an integer of 0 or more. Y is an integer of 1 or more. R ¹³ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, or An alkylene group, a branched or unbranched alkenyl group or alkenylene group having 2 to 30 carbon atoms, a branched or unbranched alkynyl group or alkynylene group having 2 to 30 carbon atoms, or a terminal of the alkyl group or alkenyl group is a hydroxyl group or R ¹⁴ represents one substituted with a carboxyl group, R ¹⁴ represents hydrogen, branched or unbranched alkylene group or alkyl group having 1 to 30 carbon atoms, branched or unbranched C 2-30 alkenylene group or alkenyl group, or A branched or unbranched alkynylene or alkynyl group having 2 to 30 carbon atoms, wherein R ¹³ and R ¹⁴ are ring structures; May be formed.)

Examples of the halogen for R ¹³ include chlorine, bromine, and fluorine.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 5 carbon atoms) of R ¹³ and R ¹⁴ include, for example, the branched or unbranched groups of R ¹¹ described above. The same group as the C1-C30 alkyl group of can be mentioned.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms) of R ¹³ and R ¹⁴ include, for example, the branched or unbranched alkylene group having 1 to 30 carbon atoms of R ^10. The same group can be mentioned.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) of R ¹³ and R ¹⁴ include, for example, the branched or unbranched alkenyl group having 2 to 30 carbon atoms of R ^11. The same group can be mentioned.

R ^13, examples of alkenylene groups branched or unbranched carbon atoms 2 to 30 ^{R 14} (preferably 2 to 12 carbon atoms), for example, a branched or unbranched alkenylene group having 2 to 30 carbon atoms of the ^{R 10} The same group can be mentioned.

Examples of the branched or unbranched alkynyl group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) of R ¹³ and R ¹⁴ include, for example, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, and heptynyl. Group, octynyl group, noninyl group, decynyl group, undecynyl group, dodecynyl group and the like.

Examples of the branched or unbranched alkynylene group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) of R ¹³ and R ¹⁴ include, for example, the branched or unbranched alkynylene group having 2 to 30 carbon atoms of R ^10. The same group can be mentioned.

In the silane coupling agent comprising the binding unit A and the binding unit B, the total number of repetitions (x + y) of the repeating number (x) of the bonding unit A and the repeating number (y) of the bonding unit B is in the range of 3 to 300. Is preferred. Within this range and when x is 1 or more, since the mercaptosilane of the bond unit B is covered by —C ₇ H ₁₅ of the bond unit A, it is possible to suppress the scorch time from being shortened, and to use silica and rubber components And good reactivity can be ensured.

For example, NXT-Z30, NXT-Z45, NXT-Z60, or NXT-Z100 manufactured by Momentive can be used as the silane coupling agent composed of the binding unit A and the binding unit B. These may be used alone or in combination of two or more.

The content of the silane coupling agent represented by the above formula (2) and / or the coupling unit A represented by the above formula (3) and the coupling unit B represented by the above formula (4) is: Preferably it is 4 mass parts or more with respect to 100 mass parts of silica, More preferably, it is 6 mass parts or more, More preferably, it is 8 mass parts or more. If it is less than 4 parts by mass, the fracture strength tends to be greatly reduced. Moreover, this content is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of silica. When it exceeds 15 parts by mass, there is a tendency that effects such as improvement in breaking strength (breaking characteristics) and reduction in rolling resistance cannot be obtained sufficiently by blending a silane coupling agent.
The content is a combination of a silane coupling agent represented by the above formula (2) and a silane coupling agent comprising the binding unit A represented by the above formula (3) and the coupling unit B represented by the above formula (4). When doing, it means the total content.

In this invention, it is preferable to mix | blend the vulcanization accelerator represented by following formula (5). Thereby, even if it is a case where the silane coupling agent which has a mercapto group is used, generation | occurrence | production of scorch can be suppressed and low exothermic property (low fuel consumption property) and rubber strength (tear strength) can be improved with good balance.
When a silane coupling agent composed of the binding unit A represented by the above formula (3) and the coupling unit B represented by the above formula (4) is used, even when x is 0 (that is, the binding unit A exists) However, the occurrence of scorch can be suppressed by the vulcanization accelerator represented by the following formula (5).
On the other hand, when x is not 0 (that is, the bonding unit A exists), the vulcanization accelerator represented by the following formula (5) and the bonding unit A can synergistically suppress the generation of scorch.

Z in the above formula (5) represents an integer of 1 to 8 (preferably 1 to 5, more preferably 1 to 3). If z is 0, the scorch time tends to be short and workability tends to deteriorate, and if z is 9 or more, the vulcanization rate tends to slow, which is not preferable.

Examples of the vulcanization accelerator represented by the above formula (5) include TBzTD (tetrabenzylthiuram disulfide) manufactured by Flexis. These may be used alone or in combination of two or more.

The blending amount of the vulcanization accelerator represented by the above formula (5) is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 0.2 parts by mass, the vulcanization rate becomes too slow, which is not preferable. The blending amount is preferably 6.0 parts by mass or less, more preferably 5.0 parts by mass or less, still more preferably 4.0 parts by mass or less, particularly preferably 3.0 parts by mass or less, and most preferably 2 parts by mass. 0.0 part by mass or less, particularly preferably 1.0 part by mass or less. If it exceeds 6.0 parts by mass, the vulcanization rate becomes too fast and the workability may be deteriorated.

In the present invention, other vulcanization accelerators may be used in combination with the vulcanization accelerator represented by the above formula (5). Other vulcanization accelerators that can be used in combination include, for example, sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine or aldehyde-ammonia, imidazoline, or xanthate. And vulcanization accelerators. Of these, sulfenamide-based vulcanization accelerators are preferred because they are suitable for scorch time and vulcanization speed and advantageous for rubber strength.

Examples of the sulfenamide vulcanization accelerator include N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N, N And '-dicyclohexyl-2-benzothiazolylsulfenamide (DZ). Among these, TBBS is preferable because the scorch time and the vulcanization speed are appropriate.

In the present invention, carbon black may be blended. Thereby, the intensity | strength of rubber | gum can be improved. Examples of carbon black that can be used include GPF, FEF, HAF, ISAF, and SAF, but are not particularly limited. Carbon black may be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 30 m ² / g or more, and more preferably 70 m ² / g or more. If it is less than 30 m ² / g, there is a tendency that sufficient reinforcing properties cannot be obtained. Further, the nitrogen adsorption specific surface area of carbon black is preferably 250 meters ² / g or less, more preferably ^{150m 2 / g, 100m 2 /} g or less is more preferable. If it exceeds 250 m ² / g, the viscosity at the time of unvulcanization becomes very high, and the workability tends to deteriorate, or the fuel efficiency tends to deteriorate.
In addition, the nitrogen adsorption specific surface area of carbon black is calculated | required by A method of JISK6217.

When the rubber composition of the present invention contains carbon black, the content of carbon black is preferably 10 parts by mass or more, more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 10 parts by mass, sufficient reinforcing properties tend not to be obtained. Further, the carbon black content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less. If it exceeds 60 parts by mass, heat generation will increase and fuel economy tends to deteriorate.

In addition to the above components, the rubber composition of the present invention includes compounding agents generally used in the production of rubber compositions, such as reinforcing fillers such as clay, stearic acid, zinc oxide, various anti-aging agents, oils A softening agent such as wax, a vulcanizing agent such as wax, sulfur and the like can be appropriately blended.

As a method for producing the rubber composition of the present invention, a known method can be used. For example, the above components are kneaded using a rubber kneader such as an open roll or a Banbury mixer, and then vulcanized. Can be manufactured.

The rubber composition of the present invention is used for a chafer formed so as to form a tire lumen surface. With this member, the air permeation amount can be reduced and the tire internal pressure can be maintained. Specifically, it is used for the members shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2008-291091, FIGS. 1-2 of Japanese Patent Application Laid-Open No. 2007-160980, and the like.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition blended with various additives as necessary is extruded according to the shape of the tire chafer at the unvulcanized stage, and molded by a normal method on a tire molding machine, Bonding together with other tire members forms an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce a tire.

The tire of the present invention is suitably used as a passenger car tire, bus tire, truck tire, and the like.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

シランカップリング剤（３）：Ｍｏｍｅｎｔｉｖｅ社製のＮＸＴ−Ｚ１００（結合単位Ｂのみからなる重合体（上記式（３）、（４）において、結合単位Ａ：０モル％（ｘ＝０）、結合単位Ｂ：１００モル％、ｘ＋ｙ：１００））
プロセスオイル：出光興産（株）製のダイアナプロセスＰＳ３２
ワックス：大内新興化学工業（株）製のサンノックワックス
老化防止剤：フレキシス社製のサントフレックス１３（Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン）
ステアリン酸：日油（株）製のステアリン酸「桐」
酸化亜鉛：三井金属鉱業（株）製の酸化亜鉛１号
硫黄：軽井沢精錬所（株）製の硫黄
加硫促進剤（１）：大内新興化学工業（株）製のノクセラーＮＳ（Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド）
加硫促進剤（２）：フレキシス社製のＴＢｚＴＤ（テトラベンジルチウラムジスルフィド、上記式（５）のｚ＝２） Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
NR: TSR20
BR (1): BR150B manufactured by Ube Industries, Ltd. (cis content 97% by mass, unmodified)
BR (2): Modified butadiene rubber manufactured by Sumitomo Chemical Co., Ltd. (vinyl content 15% by mass, R ¹ , R ² and R ^{3 of} formula (1) = — OCH ₃ , R ⁴ and R ⁵ = —CH ₂ CH ₃ , n = 3)
Silica: Z115Gr (N ₂ SA: 112 m ² / g) manufactured by Rhodia Japan
Carbon black: Diamond Black N330 (N ₂ SA: 75 m ² / g) manufactured by Mitsubishi Chemical Corporation
Silane coupling agent (1): Si75 (bis (3-triethoxysilylpropyl) disulfide) manufactured by Evonik Degussa
Silane coupling agent (2): Si363 manufactured by Evonik Degussa (silane coupling agent represented by the following formula (R ^{6 in the} above formula (2) = — O— (C ₂ H ₄ —O) ₅ —C) _{^{13 H 27, R 7 = C}} 2 H 5 -O-, R 8 = -O- (C 2 H 4 -O) 5 -C 13 H 27, R 9 = -C 3 H 6 -))

Silane coupling agent (3): NXT-Z100 manufactured by Momentive (polymer consisting only of bonding unit B (in the above formulas (3) and (4), bonding unit A: 0 mol% (x = 0), bonding) Unit B: 100 mol%, x + y: 100))
Process oil: Diana Process PS32 manufactured by Idemitsu Kosan Co., Ltd.
Wax: Sannoc Wax anti-aging agent manufactured by Ouchi Shinsei Chemical Industry Co., Ltd .: Santoflex 13 (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Flexis
Stearic acid: Stearic acid “paulownia” manufactured by NOF Corporation
Zinc oxide: Zinc oxide No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Sulfur vulcanization accelerator manufactured by Karuizawa Smelter Co., Ltd. (1): Noxeller NS -Butyl-2-benzothiazolylsulfenamide)
Vulcanization accelerator (2): TBzTD (tetrabenzylthiuram disulfide, z = 2 in the above formula (5)) manufactured by Flexis

Examples 1-6 and Comparative Examples 1-7
In accordance with the formulation shown in Table 1, materials other than sulfur and a vulcanization accelerator were kneaded for 4 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 3 minutes at 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition.
Further, the obtained unvulcanized rubber composition was rolled into a sheet and then press vulcanized with a mold at 175 ° C. and 21 kgf / cm ² for 15 minutes to obtain a vulcanized rubber sheet.
Further, the obtained unvulcanized rubber composition is molded into a chafer shape, bonded to other tire members, molded into a tire, and vulcanized at 170 ° C. for 12 minutes (tire size: 255). / 40R20).

The following evaluation was performed about the obtained vulcanized rubber sheet and the tire for a test. The results are shown in Table 1.

(Viscoelasticity test)
Using a viscoelastic spectrometer VES-F-3 (manufactured by Iwamoto Seisakusho Co., Ltd.) under the conditions of a temperature of 60 ° C., an initial strain of 10%, a dynamic strain of 2%, and a frequency of 10 Hz, Loss tangent) was measured. The smaller tan δ, the better the fuel efficiency.

(Rubber strength (Tear strength))
With respect to the vulcanized rubber sheet, a tear test was performed at room temperature (25 ° C.) using an angled test piece without cut according to JIS K6252, and the tear strength (kN / m) was measured. The higher the tear strength, the higher the rubber strength and the less the damage.

(Rim removal test)
Using a normal tire changer, the test tire was removed from the rim, and the chafer part was visually inspected for damage (O: no damage, X: damaged rubber, etc.).

Silane composed of a modified butadiene rubber, silica, a silane coupling agent represented by the above formula (2) and / or a bond unit A represented by the above formula (3) and a bond unit B represented by the above formula (4). Examples including the coupling agent were able to improve the low heat build-up (low fuel consumption) and rubber strength (tear strength) in a well-balanced manner. Also, no damage was seen when the tire was removed from the rim.

On the other hand, Comparative Examples 1 to 3 in which the silane coupling agent and the modified butadiene rubber are not blended, Comparative Examples 4 to 6 in which the silane coupling agent is not blended, and Comparative Example 7 in which the modified butadiene rubber is not blended are In comparison, the low heat build-up (low fuel consumption) and the rubber strength (tear strength) were inferior. Damage was also observed when the tire was removed from the rim.

Claims (4)

A rubber component containing a butadiene rubber modified with a compound represented by the following formula (1);
Silica,
A chafer comprising a silane coupling agent represented by the following formula (2) and / or a binding unit A represented by the following formula (3) and a silane coupling agent comprising a binding unit B represented by the following formula (4) Rubber composition.

(In formula (1), R ¹ , R ² and R ³ are the same or different and are branched or unbranched alkyl groups, branched or unbranched alkoxy groups, branched or unbranched silyloxy groups, branched or unbranched. R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a branched or unbranched alkyl group, and n represents an integer.

(In Formula (2), R ⁶ is —O— (R ¹⁰ —O) _m —R ¹¹ (m R ^{10 s} are the same or different and are branched or unbranched C 1-30 divalent divalent) R ¹¹ represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms. Represents an aralkyl group of ˜30. M represents an integer of 1 to 30.) R ⁷ and R ⁸ are the same or different and are the same group as R ⁶ , branched or unbranched. An alkyl group having 1 to 12 carbon atoms or —O—R ¹² (R ¹² is a hydrogen atom, a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, C6-C30 aryl group or C7-C30 aralkyl .R ⁹ represents a group represented by a group.) Represents a branched or unbranched alkylene group having 1 to 30 carbon atoms.)

(In the formulas (3) and (4), x is an integer of 0 or more. Y is an integer of 1 or more. R ¹³ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, or An alkylene group, a branched or unbranched alkenyl group or alkenylene group having 2 to 30 carbon atoms, a branched or unbranched alkynyl group or alkynylene group having 2 to 30 carbon atoms, or a terminal of the alkyl group or alkenyl group is a hydroxyl group or R ¹⁴ represents one substituted with a carboxyl group, R ¹⁴ represents hydrogen, branched or unbranched alkylene group or alkyl group having 1 to 30 carbon atoms, branched or unbranched C 2-30 alkenylene group or alkenyl group, or A branched or unbranched alkynylene or alkynyl group having 2 to 30 carbon atoms, wherein R ¹³ and R ¹⁴ are ring structures; May be formed.) The rubber composition for chafers of Claim 1 containing the vulcanization accelerator represented by following formula (5).

(In formula (5), z represents an integer of 1 to 8.) The rubber composition for chafers according to claim 1 or 2, wherein the content of the butadiene rubber modified with the compound represented by the formula (1) in 100% by mass of the rubber component is 20% by mass or more. The pneumatic tire which has a chafer produced using the rubber composition in any one of Claims 1-3.