JP5899050B2 - Rubber composition and tire - Google Patents

Description

  The present invention relates to a rubber composition and a tire. A rubber component obtained by polymerizing a conjugated diene compound in the presence of an organic alkali metal catalyst in an inert organic solvent is widely used. In order to improve the mechanical strength and wear resistance of the rubber component, rubber compositions in which an inorganic filler such as silica, calcium carbonate, magnesium carbonate or the like is blended with the rubber component are also widely used. The present invention relates to a rubber composition in which an inorganic filler is uniformly dispersed in a rubber component, and a tire using the rubber composition.

  Conventionally, as a rubber composition as described above, a rubber component containing wet silica is known (for example, see Patent Documents 1 to 4). However, wet silica has a tendency to aggregate particles due to hydrogen bonding of silanol groups, which are surface functional groups, and has poor dispersibility in the rubber component. In order to disperse silica in the rubber component, a kneading time is required. There is a problem that it needs to be long. Moreover, the dispersion of silica in the rubber component still tends to be insufficient, and the resulting rubber composition has a high Mooney viscosity, resulting in inferior processability, and the surface of the silica particles is acidic. Further, since the basic substance used as a vulcanization accelerator is adsorbed, there is a problem that the rubber composition is not sufficiently vulcanized.

  Therefore, conventionally, various methods for uniformly dispersing an inorganic filler such as silica in a rubber component have been tried. This includes, for example, 1) a method in which the terminal of the conjugated diene polymer is modified with a halogenated alkoxysilane derivative (see, for example, Patent Document 5), and 2) a method in which the conjugated diene polymer is modified by reacting with an aminosilane compound. (See, for example, Patent Document 6) 3) Method of modifying the terminal of a conjugated diene polymer with γ-glycidoxypropyltrimethoxysilane or the like (for example, see Patent Document 7), 4) In a conjugated diene polymer For example, a method of introducing an alkoxysilane structure (see, for example, Patent Document 8) has been proposed. However, in these conventional methods, the inorganic filler cannot be sufficiently uniformly dispersed in the rubber component, and as a result, the mechanical strength, wear resistance, etc. of the molded product obtained from such a rubber composition are insufficient. There is a problem.

  In order to improve the above problems, a method using silica whose surface has been treated with a hydrophobizing agent together with a silane coupling agent (see, for example, Patent Document 9), a method using hydrophobic precipitated silicic acid together with a silane coupling agent (For example, refer to Patent Document 10), a method using a specially shaped silica together with a silane coupling agent (for example, refer to Patent Document 11), etc. have been proposed, but the effects of any conventional methods are still insufficient. There's a problem.

Japanese Patent Laid-Open No. 06-248116 Japanese Patent Application Laid-Open No. 07-070369 Japanese Patent Laid-Open No. 08-245838 Japanese Patent Laid-Open No. 03-252431 JP-A-62-227908 JP-A 63-186748 Japanese Patent Laid-Open No. 09-087426 JP 2010-202769 A Japanese Patent Laid-Open No. 06-248116 Japanese Patent Laid-Open No. 06-157825 JP 2006-37046 A

  The problem to be solved by the present invention is to provide a rubber composition having excellent low heat generation, wear resistance and processability by sufficiently uniformly dispersing an inorganic filler such as silica or carbon black in a rubber component. In addition, the present invention is to provide a tire having excellent fuel efficiency and steering stability by using such a rubber composition.

  As a result of researches to solve the above problems, the present inventors are excellent in the interaction with an inorganic filler in a conjugated diene polymer as a dispersant for an inorganic filler to be blended with a rubber component together with an inorganic filler. It has been found that the use of a material having a specific structure is correctly used.

That is, the present invention is a rubber composition in which at least an inorganic filler , a dispersant for inorganic filler, and a silane coupling agent are blended with a rubber component, and the dispersant for inorganic filler has 1,2 bonds in the molecule. In the conjugated diene polymer having 85 mol% or more of the following structural unit: a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2 and a structural unit represented by the following chemical formula 3 one or der those comprising more than from the introduced modified conjugated diene polymer is, characterized in that blended with the rubber component per 100 parts by silane coupling agent in a proportion of 0.5 to 50 parts by weight of It relates to a rubber composition.

In chemical formula 1, chemical formula 2 and chemical formula 3,
R ¹ to R ¹⁰ , R ¹⁴ , R ¹⁵ : a hydrocarbon group having 1 to 20 carbon atoms R ¹¹ to R ¹³ : a hydrocarbon group having 1 to 10 carbon atoms X ¹ to X ³ : Si, Sn or Ge
p, q, r: integers from 1 to 3

  The present invention also relates to a tire characterized by being molded using the rubber composition according to the present invention.

  The rubber composition according to the present invention is obtained by blending a rubber component with at least an inorganic filler and a dispersant for inorganic filler. First, the inorganic filler dispersant (hereinafter referred to as the dispersant of the present invention) used in the rubber composition according to the present invention will be described. The dispersant of the present invention is for uniformly dispersing an inorganic filler in a rubber component, and is represented by a structural unit represented by Chemical Formula 1, a structural unit represented by Chemical Formula 2, and Chemical Formula 3 in a conjugated diene polymer. It is composed of a modified conjugated diene polymer into which one or more of the structural units selected from the structural units are introduced. In the conjugated diene polymer, the structural units represented by Chemical Formula 1 and Chemical Formula 2 are shown. Preferred are those comprising a modified conjugated diene polymer introduced with a structural unit, and further comprising a modified conjugated diene polymer obtained by introducing all of these structural units with the structural unit represented by Chemical Formula 3 added. Is preferred.

In the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 2, and the structural unit represented by Chemical Formula ³ , R ^{1 to} R ³ are each a hydrocarbon group having 1 to 20 carbon atoms. Among these, a hydrocarbon group having 1 to 11 carbon atoms is preferable, and includes 1) an alkylene group such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octatylene, nonylene, decylene, and undecylene, and 2) ethene. , Alkenyl groups such as propene, butene, pentene, hexene, heptene, octene, 3) alkynyl groups such as ethyne, propyne, butyne, pentyne, hexyne, heptine, octyne, etc. 4) fragrances such as benzene, methylbenzene, ethylbenzene, styrene And a hydrocarbon group obtained by removing two hydrogens from the group hydrocarbon compound.

In the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 2, and the structural unit represented by Chemical Formula 3, R ^{4 to} R ⁹ are each a hydrocarbon group having 1 to 20 carbon atoms. Among these, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and includes 1) methyl group, ethyl group, propyl group, butyl group, 2) ethenyl group, propenyl group, ptenyl group, and 3) ethynyl group, propynyl. Group, butynyl group and the like.

In the structural unit represented by Chemical Formula 1, R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms. Especially, a C1-C4 hydrocarbon group is preferable.

In the structural unit represented by Chemical Formula 2 and the structural unit represented by Chemical Formula 3, R ^{11 to} R ¹³ are each a hydrocarbon group having 1 to 10 carbon atoms.

In the structural unit represented by Chemical Formula 3, R ¹⁴ and R ¹⁵ are hydrocarbon groups having 1 to 20 carbon atoms.

In the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 2, and the structural unit represented by Chemical Formula ³ , X ^{1 to} X ³ are Si, Sn, or Ge. Although it depends on the inorganic filler used, when the inorganic filler is silica, X ^{1 to} X ³ are preferably Si.

  Examples of the conjugated diene polymer used in the dispersant of the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, cyclopentadiene, 2,3-dimethyl-1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-heptadiene, 1,6-heptadiene, 2-methyl-1,3-heptadiene, 3- Methyl-1,4-heptadiene, 1,3,5-heptatriene, 5-methyl-1,3,6-heptatriene, cycloheptatriene, 1,7-octadiene, 1,3-octadiene, 3,7-dimethyl- 1,6-octadiene, 7,7-dimethyl-2,5-octadiene, 1,2-cyclooctadiene, 1,5-cyclooctadiene and One or two or more monomers selected from 1,3,5-cyclooctatriene may be (co) polymerized, but styrene or acrylonitrile may be used as a monomer other than these monomers. It may be polymerized.

Among them, the conjugated diene polymer used for the dispersant of the present invention includes one or more monomers selected from 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene. the (co) obtained by polymerization is not preferable. Incidentally, the conjugated diene polymer to be subjected to dispersing agent of the present invention are those having the structural unit of 1,2 bonds is 85 mol% or more in the molecule.

  The number average molecular weight of the conjugated diene polymer used for the dispersant of the present invention is not particularly limited, but is preferably a number average molecular weight of 200 to 100,000, and more preferably a number average molecular weight of 500 to 10,000. In addition, in this invention, a number average molecular weight is a number average molecular weight of polystyrene conversion by GPC (gel permeation chromatography) method.

  The number average molecular weight of the modified conjugated diene polymer used as the dispersant of the present invention is not particularly limited, but is preferably a number average molecular weight of 300 to 200,000, more preferably a number average molecular weight of 700 to 20000. .

The dispersant of the present invention comprises one or two or more structural units selected from the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 2 and the structural unit represented by Chemical Formula 3 in the conjugated diene polymer. It can be obtained by the method of introduction. In order to react with the conjugated diene polymer and introduce a structural unit selected from the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 2 and the structural unit represented by Chemical Formula 3 into the conjugated diene polymer. For the compound, a compound represented by the following chemical formula 4 having a mercapto group in the molecule can be used.

In chemical formula 4,
R ¹⁶ ~ R ^18: a hydrocarbon group having 1 to 20 carbon atoms X ^4: Si, Sn or Ge
n: an integer from 1 to 3

R ^{16 to} R ¹⁸ in Chemical Formula ⁴ are the same as those described above for R ^{1 to} R ⁹ in Chemical Formula 1 to Chemical Formula ³ , and X ⁴ is the same as described above for X ^{1 to} X ³ . Among these, R ¹⁶ is preferably a hydrocarbon group having 1 to 11 carbon atoms, and R ¹⁷ and R ¹⁸ are preferably hydrocarbon groups having 1 to 4 carbon atoms.

  Examples of the compound represented by Chemical Formula 4 having a mercapto group in the molecule include a silane compound having a mercapto group in the molecule, a tin compound having a mercapto group in the molecule, and a germanium compound having a mercapto group in the molecule. Especially, the silane compound which has a mercapto group in a molecule | numerator, and the tin compound which has a mercapto group in a molecule | numerator are preferable, and the silane compound which has a mercapto group in a molecule | numerator is more preferable.

  Examples of the silane compound having a mercapto group in the molecule include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and 3-mercaptopropyldimethoxymethyl. Silane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptodimethoxyethylsilane, 3-mercaptodiethoxyethylsilane, 3-3-mercaptopropylmethoxydimethylsilane, 3-mercaptopropylethoxydimethylsilane, mercaptomethylenemethyldiethoxysilane , Mercaptomethylenetriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, 2-mercaptoethylethoxydimethylsilane, 11-mercaptoounde Le trimethoxysilane, 11-mercaptoundecyl dimethoxymethylsilane, 11-mercaptoundecyl methoxy dimethylsilane, 11 mercaptoundecyl triethoxy silane, such as 11-mercaptoundecyl DEMS are exemplified. These silane compounds can be used alone or in combination of two or more.

  The reaction ratio between the conjugated diene polymer and the compound represented by Chemical formula 4 having a mercapto group in the molecule is not particularly limited, but the conjugated diene polymer / compound represented by Chemical formula = 99/1 to 10/90 ( (Weight ratio) is preferable, and from the viewpoint of reaction time, it is more preferable to perform the reaction at a compound represented by conjugated diene polymer / chemical formula = 95/5 to 15/85 (weight ratio).

  The modified conjugated diene polymer as the dispersant of the present invention is obtained by reacting the compound represented by Chemical Formula 4 with the conjugated diene polymer by heat in an inert gas atmosphere in which no catalyst is present. Can be obtained. Specifically, for example, a conjugated diene polymer obtained by (co) polymerizing one or two or more monomers selected from 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene. It can be obtained by heating to 120 to 250 ° C. and dropping and reacting the compound represented by Chemical Formula 4 having a mercapto group in the molecule. The reaction temperature is preferably 140 to 200 ° C. When the reaction temperature is higher than 200 ° C., the resulting dispersant is likely to be colored. Conversely, when the reaction temperature is lower than 140 ° C., the reaction is difficult to proceed. When the reaction is carried out by increasing the ratio of the compound represented by Chemical Formula 4 with respect to the conjugated diene polymer, from the viewpoint of reaction time and reaction rate, it is converted into a diene polymer under pressure using an autoclave. It is more preferable to react with the compound represented by 4.

  As described above, the compound represented by Chemical Formula 4 is reacted with the conjugated diene polymer to obtain a modified conjugated diene polymer as the dispersant of the present invention. The reaction rate when both are reacted is not particularly limited, but is preferably 85% or more, and more preferably 90% or more.

  Examples of the rubber component used in the rubber composition according to the present invention include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, and acrylonitrile. Examples thereof include one or two or more selected from butadiene rubber, acrylonitrile-styrene-butadiene rubber, chloroprene rubber, halogenated butyl rubber, and a copolymer of a styrene compound having a methyl halide group and isoprene. Among these, those selected from natural rubber and diene rubber are preferable.

  Examples of the inorganic filler used in the rubber composition according to the present invention include one or more selected from silica, carbon black, calcium carbonate, magnesium carbonate, and alumina. Among these, those selected from silica and carbon black are preferable.

The rubber composition according to the present invention, As described above, by blending a dispersant at least an inorganic filler and the present invention in the rubber component is obtained by further compounding a silane coupling agent.

  The type of the silane coupling agent used in the rubber composition according to the present invention is not particularly limited, and examples of the silane coupling agent include a compound represented by the following chemical formula 5, a compound represented by the following chemical formula 6, and the following chemical formula. One or two or more selected from the compound represented by 7 and the compound represented by the following chemical formula 8 are preferred.

In chemical formula 5,
R ¹⁶ : R ²¹ O—, R ²¹ C (═O) O—, R ²¹ R ²² C═NO—, R ²¹ R ²² NO—, R ²¹ R ²² N— or — (OSiR ²¹ R ²² ) _n ( An organic group represented by OSiR ²¹ R ²² R ²³ ) (wherein R ^{21 to} R ²³ are each independently an alkyl group, a cycloalkyl group, or an alkenyl group having 1 to 18 carbon atoms and n = 0 to 10). , Cycloalkenyl group or aryl group R ¹⁷ : hydrogen atom, all of which have 1 to 18 carbon atoms, cycloalkyl group, alkenyl group, cycloalkenyl group or aryl group R ¹⁸ : — [O (R ²⁴ O) _m ] _0.5 - organic group represented by ^{(wherein, R 24} is an alkylene group or a cycloalkylene group x is any integer from 1 to 18 and m = 1 to 4 carbon atoms, y, z: either x + y 2z = 3,0 ≦ x ≦ 3,0 ≦ y ≦ 2,0 ≦ z ≦ 1 for satisfying the relationship integer R ^19: an alkylene group each a 1 to 18 carbon atoms, cycloalkylene group, cycloalkylalkylene group, Alkenylene group, arylene group or aralkylene group R ²⁰ : Any alkyl group having 1 to 18 carbon atoms, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group or aralkyl group

In Chemical Formula 6,
A: chlorine atom or a _C n _{H 2n +} 1 O- organic group represented (where, n is an integer of 1 to 3)
B: an alkyl group having 1 to 3 carbon atoms m: an integer of 1 to 3 a: an integer of 1 to 9 b: an integer of 1 or more However, when m is 1, B may be the same or different from each other In addition, when m is 2 or 3, A may be the same or different from each other.

In Chemical Formula 7,
A: chlorine atom or a _C n _{H 2n +} 1 O- organic group represented (where, n is an integer of 1 to 3)
B: an alkyl group having 1 to 3 carbon atoms Y: a mercapto group, a vinyl group, an amino group, a glycidoxy group, or an epoxy group m: an integer of 1 to 3 c: an integer of 0 to 9 However, when m is 1, B is They may be the same or different from each other, and when m is 2 or 3, A may be the same or different from each other.

In chemical formula 8,
A: chlorine atom or a _C n _{H 2n +} 1 O- organic group represented (where, n is an integer of 1 to 3)
B: an alkyl group having 1 to 3 carbon atoms Z: a benzothiazolyl group, an N, N-dimethylthiocarbamoyl group or a methacryloyl group m: an integer of 1 to 3 a: an integer of 1 to 9 b: an integer of 1 or more, where m is When it is 1, B may be the same or different from each other, and when m is 2 or 3, A may be the same or different from each other.

The rubber composition according to the present invention, a dispersing agent of at least an inorganic filler and the present invention in the rubber component can be prepared by kneading a silane coupling agent further. In preparing the rubber composition according to the present invention, the inorganic filler is usually kneaded at a ratio of 5 to 200 parts by weight, preferably 10 to 100 parts by weight per 100 parts by weight of the rubber component, and the dispersant of the present invention. the usually 1 to 40 parts by weight, preferably kneaded at a ratio of 3 to 20 parts by weight, 0.5 to 50 parts by weight of a further silane coupling agent, preferably kneaded at a ratio of 2 to 25 parts by weight. These kneading can be performed by a commonly used kneader such as an open kneader such as a roll or a closed kneader such as a Banbury mixer.

  The rubber composition according to the present invention has various chemicals such as those usually used in the rubber industry association, for example, a vulcanizing agent other than sulfur, and vulcanization acceleration, as long as the effect of the dispersant of the present invention is not impaired. It can be used in combination with an agent, process oil, plasticizer, anti-aging agent, anti-scorch agent, zinc white, stearic acid, thermosetting resin, thermoplastic resin and the like.

  The tire according to the present invention is formed by a conventional method using the rubber composition according to the present invention described above. Molding means include compression molding using sheet molding material (SMC), injection molding using bulk molding material (BMC), resin transfer molding using liquid molding material (RTM), resin injection molding, reaction Examples thereof include an injection molding method (RIM) and a pultrusion molding method. Usually, when vulcanized after molding, a tire, typically an automobile tire, can be obtained.

  According to the present invention, it is possible to obtain a rubber composition in which an inorganic filler such as silica or carbon black is uniformly dispersed in a rubber component, and the rubber composition is excellent in low heat generation, wear resistance and processability. From such a rubber composition, a tire excellent in fuel efficiency and steering stability can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, unless otherwise indicated, parts are parts by mass and% is% by mass.

Test Category 1 (Synthesis of dispersant for inorganic filler)
Synthesis of Inorganic Filler Dispersant P-1 In a 1.5 L four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, a thermometer and a dropping funnel, 900 g of liquid 1, 2-polybutadiene (manufactured by Nippon Soda Co., Ltd., trade name Nisso PB-B-1000, number average molecular weight 1000) was charged and thoroughly purged with nitrogen, then the internal temperature was raised to 150 ° C. with stirring, and 100 g as a silane coupling agent 3-mercaptopropyltriethoxysilane (manufactured by Momentive Performance Materials, trade name A-1891, molecular weight 238.4) was gradually added dropwise. After completion of dropping, the mixture was further aged at 150 ° C. for 5 hours. After aging, the mixture was cooled to room temperature to obtain a colorless transparent viscous liquid modified conjugated diene polymer. This modified conjugated diene polymer had a reaction rate of over 98% and a number average molecular weight of 1,600 because the peak of the silane coupling agent as a starting material disappeared from the GPC chart. . The modified conjugated diene polymer obtained here was used as the inorganic filler dispersant P-1.

Synthesis of Inorganic Filler Dispersant P-11 Into a 2 L autoclave equipped with a pressure vessel, a stirrer, a pressure gauge, and a safety valve, 334 g of liquid 1,2-polybutadiene (manufactured by Nippon Soda Co., Ltd., as a conjugated diene polymer) Product name Nisso PB-B-3000, number average molecular weight 3000) and 666 g of 3-mercaptopropyltriethoxysilane (product of Momentive Performance Materials, trade name A-1891, molecular weight) 238.4) was charged and sufficiently substituted with nitrogen, and then a pressure of ² kg / cm ² was applied with nitrogen. Thereafter, the internal temperature was raised to 150 ° C. while stirring, and the reaction was allowed to proceed for 18 hours with nitrogen being finally applied at a pressure of 4 kg / cm ² . After the reaction, the mixture was cooled to room temperature to obtain a colorless and transparent viscous liquid modified conjugated diene polymer. This modified conjugated diene polymer had a reaction rate of over 98% and a number average molecular weight of 9,500 from the GPC chart. The modified conjugated diene polymer obtained here was used as a dispersant for inorganic filler P-11.

Synthesis of inorganic filler dispersants P-2 to P-10 and P-12 to P-34 In the same manner as inorganic filler dispersant P-1, dispersants P-2 and P for inorganic filler -7, P-8, and P-15 were obtained. In addition, other inorganic filler dispersants were obtained in the same manner as inorganic filler dispersant P-11. These contents are summarized in Table 1.

In Table 1,
* 1: Number of moles of the compound represented by Chemical Formula 4 per mole of conjugated diene polymer A-1: Liquid 1,2-polybutadiene, number average molecular weight 1000, 1,2 ratio of structural units 85% (Nippon Soda Co., Ltd., trade name PB-B-1000)
A-2: Liquid 1,2-polybutadiene, number average molecular weight 2000, ratio of 1,2-bonded structural units 90% or more (Nippon Soda Co., Ltd., trade name PB-B-2000)
A-3: Liquid 1,2-polybutadiene, number average molecular weight 3000, ratio of 1,2-bond constituent units 90% or more (Nippon Soda Co., Ltd., trade name PB-B-3000)
A-4: Glycol-terminated glycol 1,2-polybutadiene, number average molecular weight 1000, 1,2 bond constituent unit ratio 85% or more (Nippon Soda Co., Ltd., trade name PB-G-1000)
A-5: Liquid both-end glycol 1,2-polybutadiene, number average molecular weight 2000, ratio of 1,2-bonded structural unit 85% or more (Nippon Soda Co., Ltd., trade name PB-G-2000)
A-6: Liquid both-end glycol 1,2-polybutadiene, number average molecular weight 3000, 1, 90% or more of structural units of 1 bond (Nippon Soda Co., Ltd., trade name PB-G-3000)
A-7: Liquid end-terminal carboxylic acid 1,2-polybutadiene, number-average molecular weight 1000, 1, proportion of structural units of 1,2 bonds 85% or more (Nippon Soda Co., Ltd., trade name PB-C-1000)
A-8: Liquid 1,2-polybutadiene, number average molecular weight 5200, ratio of 1,2-bond constituent units 90% or more (Sartomer, trade name Ricon154)
A-9: Liquid 1,4-polybutadiene, number average molecular weight 8000, ratio of structural units of 1,4 bonds 90% (product name: LBR-307, manufactured by Kuraray Co., Ltd.)
A-10: Liquid 1,4-polybutadiene, number average molecular weight 26000, proportion of constituent units of 1,4 bonds 90% (product name: LBR-305, manufactured by Kuraray Co., Ltd.)
A-11: Liquid 1,4-polybutadiene, number average molecular weight 44000, ratio of constituent units of 1,4 bonds 90% (product name: LBR-300, manufactured by Kuraray Co., Ltd.)
A-12: Liquid 1,2-polybutadiene, number average molecular weight 8000, proportion of 1,2-bond constituent units 28% (product name Ricon 134, manufactured by Sartomer)
A-13: Liquid polyisoprene, number average molecular weight 28000 (manufactured by Kuraray Co., Ltd., trade name LIR-30)
A-14: Liquid polyisoprene, number average molecular weight 54000 (manufactured by Kuraray Co., Ltd., trade name LIR-50)
A-15: Liquid both-end glycol polyisoprene, number average molecular weight 2500 (made by Idemitsu Kosan Co., Ltd., trade name Poly.ip)
A-16: Liquid styrene-butadiene copolymer, number average molecular weight 8500 (manufactured by Kuraray Co., Ltd., trade name L-SBR-820)

B-1: 3-mercaptopropyltriethoxysilane, molecular weight 238.42 (trade name A-1891 manufactured by Momentive Performance Materials)
B-2: 3-mercaptopropylmethyldiethoxysilane, molecular weight 208.42 (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-3: 3-mercaptopropyltrimethoxysilane, molecular weight 196.34 (trade name KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-4: 3-mercaptopropylmethyldimethoxysilane, molecular weight 180.34 (trade name KBM-802, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-5: 11-mercaptoundecyltrimethoxysilane, molecular weight 350.63 (trade name SIM6480.0, manufactured by Gelest, Inc.)
B-6: Mercaptomethylenemethyldiethoxysilane, molecular weight 180.28 (trade name SIM6473.0 manufactured by Gelest, Inc.)

Test category 2 (preparation, molding and evaluation of rubber composition)
In the proportions listed in Table 2, natural rubber (variety RSS3), butadiene rubber (trade name BR01 manufactured by JSR), silica as an inorganic filler (trade name Nibusil AQ, manufactured by Tosoh Silica Co.), A rubber composition was prepared by blending the mixture at the stated ratio and the dispersant for inorganic filler obtained in Test Category 1 and kneading the mixture with a closed Banbury mixer. These rubber compositions were molded into a plate shape, and the silica dispersion state of each molded product was evaluated as follows. Further, the tensile strength at break and the elongation at break were measured according to JIS-K6301, and the wear resistance index was further measured by using a Lambone-type wear tester to measure the amount of wear at a slip rate of 60% at a room temperature. It was determined by comparing the abrasion resistance of the molded product of the rubber composition as 100. A larger value is better. The results are summarized in Table 2. In Table 2, Comparative Example 1 is a blank not using the inorganic filler dispersant.

The dispersion state of the silica of the molded product was evaluated as follows.
Evaluation of dispersion state of silica: The molded product was cut with a microtome, and the dispersion state of silica on the cut surface was observed with an SEM with EDX (scanning electron microscope with energy dispersive X-ray analyzer) and evaluated according to the following criteria. .
○: Dispersed in a state close to primary particles.
Δ: Some aggregated particles are observed.
X: Almost only aggregated particles, no primary particles are observed.
The particle diameter of the primary particles was the median diameter of a laser scattering / diffraction type particle size distribution meter.

In Table 2 and Table 3,
Silica: Nibsil AQ, trade name by Tosoh Silica
Mineral oil: Aroma oil (trade name JOMO X140 manufactured by Japan Energy)
Anti-aging agent: N-phenyl-N- (1,3-dimethylbutyl) -p-phenylenediamine (trade name NOCRACK 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.)
Stearic acid: Trade name manufactured by Kao Corporation Industrial stearate Zinc flower: Trade name Zinc flower No. 1 manufactured by Mitsui Kinzoku Mining Co., Ltd. Wax: Paraffin wax (trade name Ozoace 0355 manufactured by Nippon Seiwa Co., Ltd.)
Vulcanization accelerator: N-tert-butyl-2-benzothiazolylsulfenamide (trade name Noxeller NS-P manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.)

  As is clear from the results in Table 2, in the rubber composition of each example using the dispersant of the present invention, silica can be uniformly dispersed in the rubber component, and as a result, the resulting rubber molded machine Strength and wear resistance index are sufficiently improved.

Test category 3 (preparation and test of rubber composition)
Each material used was kneaded in a Banbury mixer with the blending contents shown in Table 4 to prepare a rubber composition. These rubber compositions were subjected to a dynamic viscoelasticity test as described below to determine tan δ and viscosity (both indexes), and the results are summarized in Table 4. In Table 4, Comparative Example 2 is a blank not using the inorganic filler dispersant.

  Dynamic viscoelasticity test: About the rubber composition of each example, using a spectrometer (dynamic viscoelasticity measuring and testing machine) manufactured by Ueshima Seisakusho Co., Ltd., frequency 52 Hz, initial strain 10%, measurement temperature 60 ° C., dynamic strain 1% The values of tan δ and the viscosity were obtained from the above, and displayed as an index when the value of the rubber composition of Test Example 15 was taken as 100. In addition, it has shown that it is so low exothermicity that the index value of tan-delta is small.

In Table 4,
Numerical values in table: Except Tan δ and viscosity, parts by mass of materials used Solution polymerization SBR: Product name T2000 manufactured by Asahi Kasei Corporation
Carbon: Product name 80th carbon manufactured by Asahi Carbon Co. Silica: Product name manufactured by Nippon Silica Kogyo Co., Ltd. Nip seal AQ, BET surface area = 220 m ² / g
Silane compound: bis (3-triethoxysilylpropyl) disulfide Anti-aging agent 1: Trade name NOCRACK 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
Anti-aging agent 2: NOCRACK 224 manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator 1: Trade name Sunseller D manufactured by Sanshin Chemical Industry Co., Ltd.
Vulcanization accelerator 2: Trade name Sunseller DM manufactured by Sanshin Chemical Industry Co., Ltd.
Vulcanization accelerator 3: Trade name Sunseller NS, manufactured by Sanshin Chemical Industry Co., Ltd.

  As is clear from the results in Table 4, the rubber composition using the dispersant of the present invention shows that both low heat buildup and reduced viscosity can be achieved.

Claims (6)

A rubber component, a rubber composition containing at least an inorganic filler, an inorganic filler dispersants and a silane coupling agent,
In the conjugated diene polymer in which the dispersant for an inorganic filler has 85 mol% or more of 1,2-bonded structural units in the molecule, the structural unit represented by the following chemical formula 1, the structural unit represented by the chemical formula 2 der made of modified conjugated diene polymer obtained by introducing one or more structural units selected from structural units represented by 3 is,
A rubber composition comprising a silane coupling agent in a proportion of 0.5 to 50 parts by mass per 100 parts by mass of a rubber component .

(In chemical formula 1, chemical formula 2 and chemical formula 3,
^{R 1 ~R 10, R 14,} R 15: a hydrocarbon group having 1 to 20 carbon atoms R ¹¹ to R ^13: C 1 to C 10 hydrocarbon group X ¹ ~X ^3: Si, Sn or Ge
p, q, r: integers of 1 to 3)   The rubber composition according to claim 1, wherein the rubber component is selected from natural rubber and diene rubber.   The rubber composition according to claim 1 or 2, wherein an inorganic filler is blended at a ratio of 5 to 200 parts by mass per 100 parts by mass of the rubber component.   The rubber composition according to any one of claims 1 to 3, wherein the inorganic filler dispersant is blended in an amount of 1 to 40 parts by mass per 100 parts by mass of the inorganic filler. The silane coupling agent is one or more selected from a compound represented by the following chemical formula 5, a compound represented by the following chemical formula 6, a compound represented by the following chemical formula 7 and a compound represented by the following chemical formula 8 The rubber composition according to claim 1 .

(In chemical formula 5,
R ¹⁶ : R ²¹ O—, R ²¹ C (═O) O—, R ²¹ R ²² C═NO—, R ²¹ R ²² NO—, R ²¹ R ²² N— or — (OSiR ²¹ R ²² ) _n ( OSiR ²¹ R ²² R ²³ ) (wherein R ^{21 to} R ²³ are each independently an alkyl group, cycloalkyl group, or alkenyl group having 1 to 18 carbon atoms and n = 0 to 10). , Cycloalkenyl group or aryl group R ¹⁷ : hydrogen atom, all of which are alkyl groups having 1 to 18 carbon atoms, cycloalkyl group, alkenyl group, cycloalkenyl group or aryl group R ¹⁸ : — [O (R ²⁴ O) _m ] An organic group represented by _0.5- (wherein R ²⁴ is an alkylene group or a cycloalkylene group each having 1 to 18 carbon atoms and m = 1 to 4 x, y, z: all x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦ z ≦ 1 Number R ^19: an alkylene group each a 1 to 18 carbon atoms, cycloalkylene group, cycloalkylalkylene group, alkenylene group, arylene group or aralkylene group R ^20: alkyl group each a 1 to 18 carbon atoms, a cycloalkyl Group, alkenyl group, cycloalkenyl group, aryl group or aralkyl group)

(In chemical formula 6,
A: Chlorine atom or organic group represented by C _n H _{2n + 1} O— (where n is an integer of 1 to 3)
B: an alkyl group having 1 to 3 carbon atoms m: an integer of 1 to 3 a: an integer of 1 to 9 b: an integer of 1 or more However, when m is 1, B may be the same or different from each other In addition, when m is 2 or 3, A may be the same or different from each other. )

(In chemical formula 7,
A: Chlorine atom or organic group represented by C _n H _{2n + 1} O— (where n is an integer of 1 to 3)
B: an alkyl group having 1 to 3 carbon atoms Y: a mercapto group, a vinyl group, an amino group, a glycidoxy group, or an epoxy group m: an integer of 1 to 3 c: an integer of 0 to 9 However, when m is 1, B is They may be the same or different from each other, and when m is 2 or 3, A may be the same or different from each other. )

(In chemical formula 8,
A: Chlorine atom or organic group represented by C _n H _{2n + 1} O— (where n is an integer of 1 to 3)
B: an alkyl group having 1 to 3 carbon atoms Z: a benzothiazolyl group, an N, N-dimethylthiocarbamoyl group or a methacryloyl group m: an integer of 1 to 3 a: an integer of 1 to 9 b: an integer of 1 or more, where m is When it is 1, B may be the same or different from each other, and when m is 2 or 3, A may be the same or different from each other. ) A tire formed by molding using the rubber composition according to any one of claims 1 to 5 .