# US 10,501,601 B2 · Tire rubber composition and manufacturing method therefor

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- Number: US 10,501,601 B2
- Document ID: US10501601B2
- Status: Granted
- Kind: B2
- Application number: 14/893,307
- Filed: 2014-05-28
- Published: 2016-04-28
- Granted: 2019-12-10
- Earliest claimed: 2013-05-31
- Assignees: Bridgestone Corporation
- Applicants: Bridgestone Corporation
- Inventors: Noriaki Yukimura
- Web page: https://patentgrep.com/patent/US10501601B2

## CPC

- C08K 5/405: Thioureas; Derivatives thereof
- B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C 1/0016: {Compositions of the tread}
- C08K 3/04: Carbon
- C08K 3/36: Silica
- C08K 5/30: Hydrazones; Semicarbazones
- C08K 5/548: containing sulfur {(C08K5/5477 takes precedence)}
- C08L 9/06: Copolymers with styrene
- C08L 91/00: Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention provides a tire rubber composition prepared by mixing at least one rubber component selected from natural rubbers and synthetic diene rubbers (A), a filler including an inorganic filler (B), a silane coupling agent (C) and a thiosemicarbazone derivative (D), and provides a production method for a tire rubber composition, wherein the tire rubber composition is kneaded in plural stages, and in the first stage of kneading, the rubber component (A), all or part of the inorganic filler (B), all or part of the silane coupling agent (C), and the thiosemicarbazone derivative (D) are kneaded, therefore providing a tire rubber composition having improved reactivity between the coupling agent and the rubber component and excellent in low-heat-generation property and a production method for the composition.

## Claims

### Claim 1

A tire rubber composition prepared by mixing at least one rubber component comprising styrene-butadiene copolymer rubber (A), a filler comprising an inorganic filler (B), a silane coupling agent (C) and a thiosemicarbazone derivative (D),
wherein the thiosemicarbazone derivative (D) is acetonethiosemicarbazone.

### Claim 2 (depends on 1)

The tire rubber composition according to claim 1, wherein the silane coupling agent (C) is at least one compound selected from the group consisting of compounds represented by the following general formulae (II) to (IV):
(R1O)3-p(R2)pSi—R3—Sa—R3—Si(OR1)3-r(R2)r (II)
wherein plural R1's, if any, may be the same or different and each represent a substituent selected from a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms, a linear or branched alkoxylalkyl group having from 2 to 8 carbon atoms, and a hydrogen atom; plural R2's, if any, may be the same or different and each represent a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms; plural leis, if any, may be the same or different and each represent a linear or branched alkylene group having from 1 to 8 carbon atoms; a indicates from 2 to 6 as a mean value; and p and r may be the same or different and each indicate from 0 to 3 as a mean value, provided that both p and r are not 3 at the same time;
wherein R4 represents a monovalent group selected from —Cl, —Br, R9O—, R9C(═O)O—, R9R10C═NO—, R9R10CNO—, R9R10N—, and —(OSiR9R10)h(OSiR9R10R11) (where R9, R10 and R11 each represent a hydrogen atom or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; and h indicates from 1 to 4 as a mean value); R5 represents R4, a hydrogen atom, or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; R6 represents R4, R5, a hydrogen atom, or a group —[O(R12O)j]0.5 (where R12 represents an alkylene group having from 1 to 18 carbon atoms; and j indicates an integer of from 1 to 4); R7 represents a divalent hydrocarbon group having from 1 to 18 carbon atoms; R8 represents a monovalent hydrocarbon group having from 1 to 18 carbon atoms; x, y and z each indicate a number satisfying the relationship of x+y+2z=3, 0≤x≤3, 0≤y≤2, 0≤z≤1;
(R13O)3-s(R14)sSi—R15—Sk—R16—Sk—R15—Si(OR13)3-t(R14)t (IV)
wherein plural R13's, if any, may be the same or different and each represent a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms, a linear or branched alkoxylalkyl group having from 2 to 8 carbon atoms, or a hydrogen atom; plural R14's, if any, may be the same or different and each represent a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms; plural R15's, if any, may be the same or different and each represent a linear or branched alkylene group having from 1 to 8 carbon atoms; V represents a divalent group selected from general formulae (—S—R17—S—), (—R18—Sm1—R19—) and (—R20—Sm2—R21—Sm3—R22—) (where R17 to R22 each represent a divalent substituent selected from a divalent hydrocarbon group, a divalent aromatic group and a divalent organic group containing a hetero element except sulfur and oxygen, each having from 1 to 20 carbon atoms; m1, m2 and m3 each indicate from 1 to less than 4 as a mean value); plural k's may be the same or different and each indicate from 1 to 6 as a mean value; and s and t each indicate from 0 to 3 as a mean value, provided that both s and t are not 3 at the same time.

### Claim 3 (depends on 2)

The tire rubber composition according to claim 2, wherein the silane coupling agent (C) is a compound represented by the general formula (II).

### Claim 4 (depends on 1)

The tire rubber composition according to claim 1, wherein the inorganic filler (B) is silica.

### Claim 5 (depends on 1)

The tire rubber composition according to claim 1, wherein the filler contains carbon black.

### Claim 6 (depends on 1)

The tire rubber composition according to claim 1, wherein the inorganic filler (B) accounts for 40% by mass or more in the filler.

### Claim 7 (depends on 1)

A tire using the tire rubber composition of claim 1.

### Claim 8 (depends on 4)

The tire rubber composition according to claim 4, wherein the tire rubber composition is kneaded in plural stages, and
all of the rubber component (A), all or part of the silica, all or part of the silane coupling agent (C), and all of the thiosemicarbazone derivative (D) are kneaded in a first stage of kneading, or
in the first stage of kneading, as a first master batch kneading stage, all of the rubber component (A), all or part of the silica, and all or part of the silane coupling agent (C) are kneaded, spontaneously cooled and aged, and then as an intermediate stage, all of the thiosemicarbazone derivative (D) is added and further kneaded.

### Claim 9 (depends on 3)

The tire rubber composition according to claim 3, wherein
the inorganic filler (B) is silica,
the filler comprises carbon black,
the filler is incorporate in an amount of from 20 to 150 parts by mass relative to 100 parts by mass of the rubber component (A),
the inorganic filler (B) is incorporated in an amount of from 20 to 120 parts by mass relative to 100 parts by mass of the rubber component (A),
the thiosemicarbazone derivative (D) is incorporated in an amount of from 0.05 to 15 parts by mass relative to 100 parts by mass of the rubber component (A),
a ratio by mass of the thiosemicarbazone derivative (D) to the silane coupling agent (C) in the tire rubber composition is from 0.02 to 1.0, and
a ratio by mass of the silane coupling agent (C) to the inorganic filler (B) in the tire rubber composition is from 0.01 to 0.6.

### Claim 10 (depends on 9)

The tire rubber composition according to claim 9, wherein
the inorganic filler (B) is incorporated in an amount of from 30 to 100 parts by mass relative to 100 parts by mass of the rubber component (A),
the thiosemicarbazone derivative (D) is incorporated in an amount of from 0.2 to 10 parts by mass relative to 100 parts by mass of the rubber component (A),
the ratio by mass of the thiosemicarbazone derivative (D) to the silane coupling agent (C) in the tire rubber composition is from 0.04 to 0.5, and
the ratio by mass of the silane coupling agent (C) to the inorganic filler (B) in the tire rubber composition is from 0.03 to 0.2.