WO2017119254A1 - Rubber composition, rubber composition for crawlers, lug part rubber, and rubber crawler - Google Patents

Rubber composition, rubber composition for crawlers, lug part rubber, and rubber crawler Download PDF

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Publication number
WO2017119254A1
WO2017119254A1 PCT/JP2016/087296 JP2016087296W WO2017119254A1 WO 2017119254 A1 WO2017119254 A1 WO 2017119254A1 JP 2016087296 W JP2016087296 W JP 2016087296W WO 2017119254 A1 WO2017119254 A1 WO 2017119254A1
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Prior art keywords
rubber
mass
parts
recycled
rubber composition
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PCT/JP2016/087296
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French (fr)
Japanese (ja)
Inventor
祥一 谷本
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株式会社ブリヂストン
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Priority to CN201680077816.1A priority Critical patent/CN108473725A/en
Publication of WO2017119254A1 publication Critical patent/WO2017119254A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D55/00—Endless track vehicles
    • B62D55/08—Endless track units; Parts thereof
    • B62D55/18—Tracks
    • B62D55/24—Tracks of continuously flexible type, e.g. rubber belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D55/00—Endless track vehicles
    • B62D55/08—Endless track units; Parts thereof
    • B62D55/18—Tracks
    • B62D55/24—Tracks of continuously flexible type, e.g. rubber belts
    • B62D55/253—Tracks of continuously flexible type, e.g. rubber belts having elements interconnected by one or more cables or like elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L17/00—Compositions of reclaimed rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a rubber composition, a rubber composition for a crawler, a lug rubber, and a rubber crawler.
  • the rubber composition is subjected to a fine particle size treatment, and a powder rubber substantially containing only that passed through a 200-mesh sieve, Furthermore, the recycled rubber obtained by processing by an oil pan method is contained (for example, refer patent document 1).
  • a rubber composition for tires with recycled rubber in which the decrease in tensile strength and wear resistance is made as small as possible, in particular, a rubber composition for tires with recycled rubber suitable for tire treads is recycled. It is disclosed that carbon black and an oil component in the case where 10 to 50 parts by weight of recycled rubber is blended with 100 parts by weight of a diene rubber excluding rubber are blended in a blending amount obtained by a specific formula (for example, , See Patent Document 2).
  • the recycled rubber obtained from waste rubber has various performances required as rubber compared to the new rubber
  • the rubber composition obtained by mixing the recycled rubber and the new rubber is made of recycled rubber.
  • the blending amount increased, the performance easily decreased. Therefore, in order to mix recycled rubber without impairing the characteristics required for rubber products (for example, tires), the amount of recycled rubber must be reduced.
  • Patent Document 1 less than 50% by mass of new rubber
  • Patent Document 2 the recycled rubber can be used only at most up to 50% by mass of the new rubber.
  • a construction machine such as a bull tozer
  • a rubber crawler that constitutes a running part such as a bull tozer is required to have higher tensile strength, wear resistance, and the like than a tire.
  • the present invention provides a rubber composition and a rubber composition for a crawler that are excellent in tensile strength and excellent in wear resistance even when a larger amount of recycled rubber is blended than before, and excellent in tensile strength and resistance.
  • An object of the present invention is to provide a lug rubber and a rubber crawler excellent in wearability.
  • zinc oxide Carbon black in a range of (50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component) + ⁇ (recycled rubber compounding amount [parts by mass] / 200) ⁇ (10.0 to 20.0 parts by mass) ⁇ , Is a rubber composition formed by blending ⁇ 2> The rubber according to ⁇ 2
  • the diene rubber is at least one selected from the group consisting of natural rubber, isoprene rubber, and styrene butadiene rubber.
  • the raw rubber component includes 50% by mass or more of natural rubber with respect to the total mass of the raw rubber component.
  • ⁇ 5> A rubber composition for a crawler comprising the rubber composition according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 6> A rug rubber obtained from the rubber composition for a crawler according to ⁇ 5>.
  • ⁇ 7> A rubber crawler obtained from the rubber composition for a crawler according to ⁇ 5>.
  • ⁇ 8> A rubber crawler provided with the lug rubber described in ⁇ 6>.
  • a rubber composition and a rubber composition for a crawler that are excellent in tensile strength and excellent in wear resistance, and excellent in tensile strength,
  • a lug rubber and a rubber crawler excellent in wear resistance can be provided.
  • the rubber composition of the present invention comprises 100 parts by mass of an unvulcanized raw rubber component mainly composed of a diene rubber, 100 parts by mass or more and 500 parts by mass or less of a recycled rubber with respect to 100 parts by mass of the raw rubber component, (1.5 to 2.5 parts by mass with respect to 100 parts by mass of raw rubber component) + ⁇ (recycled rubber compounding amount [parts by mass] / 200) ⁇ (1.0 to 3.0 parts by mass) ⁇ Vulcanizing agent and (1.0 to 3.0 parts by mass with respect to 100 parts by mass of the raw rubber component) + ⁇ (blended amount of recycled rubber [parts by mass] / 200) ⁇ (1.0 to 4.0 masses) Parts) ⁇ and zinc oxide in the range of (50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component) + ⁇ (recycled rubber compounding amount [parts by mass] / 200) ⁇ (10.0 to 20.0) Carbon black in a range of (parts by mass) ⁇ .
  • the rubber composition of the present invention may further contain additives such as process oil and anti-aging agent.
  • additives such as process oil and anti-aging agent.
  • the conventional rubber composition containing the unvulcanized raw rubber component which is a new rubber, and recycled rubber tends to decrease the performance of the resulting rubber as the amount of recycled rubber increases. is there. This is because even if the unvulcanized raw rubber component and the vulcanized recycled rubber are kneaded and vulcanized together with a vulcanizing agent etc., the raw rubber component and the recycled rubber are not easily integrated. Since it is easy to separate, it is considered that performance such as tensile strength of rubber obtained from the rubber composition is lowered. In the vulcanization reaction of the rubber composition, the recycled rubber easily absorbs the vulcanizing agent, and the vulcanization reaction of the recycled rubber proceeds more easily than the raw rubber component.
  • the rubber derived from the recycled rubber and the rubber derived from the raw rubber component are mixed together and the resulting rubber has improved tensile strength and excellent wear resistance.
  • the structure of the rubber composition of this invention is demonstrated in detail.
  • the raw rubber component is an unvulcanized rubber component mainly composed of a diene rubber. Since rubbers that can be obtained as recycled rubber are generally made from waste tires, they are mainly composed of a diene system from the viewpoint of miscibility with recycled rubber.
  • the main component means a component that occupies 70% by mass or more with respect to the total mass of the raw rubber component, and the raw rubber component is a non-diene-based material up to 30% by mass or less with respect to the total mass of the raw rubber component. It may contain rubber.
  • Diene rubbers include natural rubber (NR), isoprene rubber (IR), (high cis) butadiene rubber [(high cis) BR], styrene butadiene rubber (SBR), ethylene-propylene rubber (EPR), and ethylene-propylene-diene rubber. (EPDM), butyl rubber (IIR), halogenated butyl rubber, chloroprene rubber, or a mixture thereof (for example, a mixture of natural rubber and styrene butadiene rubber).
  • Non-diene rubbers include butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, acrylic rubber and the like.
  • the raw rubber component preferably contains 80% by mass or more of diene rubber, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Furthermore, it is preferable that the content of natural rubber is 50% by mass or more based on the total mass of the diene rubber.
  • Recycled rubber Commercially available recycled rubber can be used as the recycled rubber used in the present invention.
  • Recycled rubber is a regenerated rubber used for automobile tires, tubes and other rubber products as defined in JIS K6313-2012, and has the same properties as this. Note that powders are excluded. Further, it is a recycled rubber that has been subjected to desulfurization treatment.
  • the type of recycled rubber may be any one selected from tube recycled rubber, tire recycled rubber, and other recycled rubber, and a plurality of types may be combined. Among these, tire recycled rubber is preferable. It is more preferable that the recycled rubber is mainly composed of a diene rubber (50% by mass or more in the rubber component of the recycled rubber). It does not specifically limit as a manufacturing method of a recycled rubber, What is necessary is just to employ
  • the recycled rubber is blended in the rubber composition in a range of 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the raw rubber component.
  • the amount of the recycled rubber is less than 100 parts by mass with respect to 100 parts by mass of the raw rubber component, the physical properties of the resulting rubber are difficult to deteriorate and various functions are easily maintained, but the recycled amount of the recycled rubber is insufficient. Yes, a larger amount of recycled rubber is not used than before.
  • the amount of the recycled rubber exceeds 500 parts by mass with respect to 100 parts by mass of the raw rubber component, the physical properties of the rubber are lowered and the various functions of the rubber cannot be maintained.
  • the amount of recycled rubber is preferably 200 parts by mass or more, more preferably 300 parts by mass or more, and 400 parts by mass with respect to 100 parts by mass of the raw rubber component. More preferably, it is more than part.
  • the vulcanizing agent is added to the rubber composition of the present invention in a basic compounding amount of 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the raw rubber component, and ⁇ (recycled rubber compounding amount [parts by mass]]. /200) ⁇ (1.0 to 3.0 parts by mass) ⁇ .
  • the basic compounding amount of the vulcanizing agent is preferably 1.7 to 2.3 parts by mass from the viewpoint of sufficiently vulcanizing the raw rubber component.
  • the added amount of the vulcanizing agent is preferably 1.2 to 3.0 parts by mass from the viewpoint of improving the wear resistance.
  • the vulcanizing agent is not particularly limited as long as it is sulfur or a compound containing sulfur.
  • Zinc oxide is added to the rubber composition of the present invention in the basis of 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the raw rubber component, and ⁇ (recycled rubber compounding amount [parts by mass] / 200) ⁇ (1.0 to 4.0 parts by mass) ⁇ .
  • the basic compounding amount of zinc oxide is preferably 2.0 to 3.0 parts by mass from the viewpoint of sufficiently vulcanizing the raw rubber component. From the viewpoint of efficiently vulcanizing the raw rubber component and reducing the difference between the vulcanizing agent absorption amount of the recycled rubber and the vulcanizing agent absorption amount of the raw rubber component, 1.
  • the amount is preferably 2 to 4.0 parts by mass.
  • the vulcanization accelerator is added to the rubber composition of the present invention in a basic compounding amount of 0.4 to 1.0 part by mass with respect to 100 parts by mass of the raw rubber component. ] / 200) ⁇ (0.1 to 1.0 part by mass) ⁇ is preferably added.
  • the basic compounding amount of the vulcanization accelerator is preferably 0.4 to 0.8 parts by mass with respect to 100 parts by mass of the raw rubber component, and the additional compounding amount is ( The amount of recycled rubber [parts by mass] / 200) ⁇ (0.4 to 0.9 parts by mass) ⁇ is preferred.
  • the vulcanization accelerator is not particularly limited.
  • M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc.
  • guanidine vulcanization accelerators such as DPG (diphenylguanidine).
  • Carbon black is added to the rubber composition of the present invention in addition to the basic compounding amount of 50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component, ⁇ (recycled rubber compounding amount [parts by mass] / 200) ⁇ ( (10.0 to 20.0 parts by mass) ⁇ .
  • the basic compounding amount of carbon black is 55 to 50% from the viewpoint of efficiently vulcanizing the raw rubber component and reducing the difference between the vulcanizing agent absorption amount of the recycled rubber and the vulcanizing agent absorption amount of the raw rubber component.
  • the amount is preferably 60 parts by mass.
  • the additional amount of carbon black is preferably 12.0 to 20.0 parts by mass from the viewpoint of the breaking strength of the vulcanized rubber.
  • the amount is preferably 10.0 to 18.0 parts by mass.
  • carbon black include standard varieties such as SAF, ISAF, HAF, FEF, GPF, SRF (furnace for rubber) and MT carbon black (pyrolytic carbon).
  • the process oil is further added to the rubber composition of the present invention in the range of ⁇ (recycled rubber compounding amount [parts by mass] / 200) ⁇ (exceeding 0 parts by mass and 20.0 parts by mass or less) ⁇ . Also good.
  • the additional amount of the process oil is preferably 5.0 to 15.0 parts by mass from the viewpoint of suppressing rubber plasticization while improving workability during kneading of the rubber composition.
  • Examples of the process oil include paraffinic, naphthenic, and aromatic process oils.
  • the rubber composition of the present invention may further contain other additives as long as the object of the present invention is not impaired.
  • additives are not particularly limited as long as they are usually contained in rubber.
  • fatty acids such as stearic acid; resins; anti-aging agents; waxes; vulcanization retarders (scorching inhibitors); Silica coupling agent; peptizer; ozone cracking inhibitor; antioxidant; clay; calcium carbonate.
  • a commercial item can be used for these.
  • the amount of the additive added can be appropriately selected by those skilled in the art as long as the object of the present invention is not impaired.
  • the blending amount is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the raw rubber component.
  • the resin examples include polyester polyol resin, dicyclopentadiene resin, rosin resin, phenol resin, xylene resin, aliphatic / alicyclic C5 petroleum resin, C5 / C9 petroleum resin, C9 petroleum resin, terpene resin, and these Examples include copolymers and modified products.
  • the amount of the resin is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the raw rubber component.
  • a known anti-aging agent can be selected and used.
  • 2,2,4-trimethyl -1,2-dihydroquinoline polymer (RD) and the like.
  • its blending amount is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the raw rubber component.
  • the blending amount is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the raw rubber component.
  • the rubber composition of the present invention can be obtained by kneading the aforementioned components.
  • the kneading method may be in accordance with a method usually carried out by those skilled in the art.
  • all components other than sulfur, a vulcanization accelerator, and zinc oxide when a vulcanization retarder is used, a vulcanization retarder is further included).
  • the rubber composition of the present invention is suitable for a rubber composition for crawlers because a rubber obtained by vulcanization is excellent in tensile strength and wear resistance.
  • a rubber obtained by vulcanization is excellent in tensile strength and wear resistance.
  • By molding the rubber composition of the present invention or the rubber composition for a crawler with a heating mold it is possible to obtain a rubber having excellent tensile strength and wear resistance.
  • By changing the heating mold a desired rubber crawler and A rubber crawler lug rubber can be obtained.
  • Examples 1 to 11 and Comparative Examples 1 to 6> In the composition shown in Table 1 and Table 2 (unit: parts by mass), each component excluding sulfur and vulcanization accelerator is kneaded at 150 ° C. with a Banbury mixer, and then sulfur and vulcanization accelerator are added and kneaded. Thus, a rubber composition was obtained, and the rubber composition was molded at a mold temperature of 150 ° C. to obtain a rubber crawler. The workability of the obtained rubber composition and the tensile strength and wear resistance of the rubber crawler were measured as follows, and the results are shown in Tables 1 and 2. The tensile strength and wear resistance of the rubber crawler were evaluated using a test piece obtained by molding the rubber composition at a mold temperature of 150 ° C., which is the same as the rubber crawler production conditions.
  • Tb Tensile strength (Tb, Trouser tear)]
  • Tb The obtained test piece was cut into the shape of a dumbbell-shaped No. 3 dumbbell-shaped test piece (JIS K6299 (2012)).
  • the obtained dumbbell-shaped test piece was required to be pulled and broken at 25 ° C. at a specified speed (500 ⁇ 25 mm / min) using a tensile test device in accordance with JIS K6251 (2010).
  • the maximum tensile force was taken as the tensile strength at break (Tb).
  • the tensile breaking strength of Comparative Example 2 is shown as an index with 100%. A larger index value indicates a higher tensile rupture strength.
  • the allowable index value is 120% or more, preferably 130% or more.
  • Anti-aging agent 6C "ANTIGENE (registered trademark) 6C "(trade name), manufactured by Sumitomo Chemical Co., Ltd. 9) Oil:” Kou Molex (registered trademark) NH-60T “(trade name), Nippon Oil Corporation 10) Ordinary sulfur (vulcanizing agent) Sulfax5 (trade name), manufactured by Tsurumi Chemical Co., Ltd. 11) Vulcanization accelerator DPG: “Noxeller (registered trademark) D” (trade name), 1,3-diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Vulcanization accelerator CZ “Noxeller (registered trademark) CZ-G” (trade name), N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd. 13)
  • Zinc oxide (Registered trademark) SR ”(trade name), manufactured by Toho Zinc Co., Ltd. 14)
  • Vulcanization retarder PVI manufactured by Monsanto, Santguard PVI (N-cyclohexylthiophthalimide)
  • the rubber composition of the present invention can be used for rubber crawlers and rubber crawler lug rubber applications.
  • Such a rubber crawler or a rubber crawler provided with a lug rubber can be used for agricultural machinery, construction machinery, or civil engineering machinery.

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Abstract

A rubber composition which is obtained by blending: 100 parts by mass of an unvulcanized starting material rubber component that is mainly composed of a diene rubber; from 100 parts by mass to 500 parts by mass (inclusive) of a regenerated rubber per 100 parts by mass of the starting material rubber component; and a vulcanizing agent within the range of (blending amount of regenerated rubber (parts by mass)/200) × (1.0-3.0 parts by mass), zinc oxide within the range of (blending amount of regenerated rubber (parts by mass)/200) × (1.0-4.0 parts by mass) and carbon black within the range of (blending amount of regenerated rubber (parts by mass)/200) × (10.0-20.0 parts by mass), respectively relative to a specific base blend. This rubber composition enables the achievement of a rubber which has excellent wear resistance and excellent tensile strength even in cases where a larger amount of a regenerated rubber is blended therein in comparison to conventional rubber compositions.

Description

ゴム組成物、クローラ用ゴム組成物、ラグ部ゴム、及びゴムクローラRubber composition, rubber composition for crawler, rug rubber, and rubber crawler
　本発明は、ゴム組成物、クローラ用ゴム組成物、ラグ部ゴム、及びゴムクローラに関する。 The present invention relates to a rubber composition, a rubber composition for a crawler, a lug rubber, and a rubber crawler.
　環境に配慮した物づくりの観点から、多くの技術分野で廃品の再利用が求められている。自動車、飛行機等のタイヤ；農業機械、建設機械、土木作業機械等の走行部に用いられるゴムクローラ等を構成するゴムも、消費が多いことから、再生ゴムを利用しながら、新たな製品を生み出す研究開発が進められている。 From the viewpoint of manufacturing with consideration for the environment, it is required to reuse waste products in many technical fields. Tires for automobiles, airplanes, etc .; rubbers used in the running parts of agricultural machines, construction machines, civil engineering machines, etc. are also consumed in large quantities, so new products are created using recycled rubber. Research and development is ongoing.
　例えば、加工性や作業性を損ねることなく、従来に比して優れたゴム物性、特に高い破壊特性を確保し得ると共に、使用済みタイヤ等のゴム製品から得られる廃ゴムのマテリアルリサイクル率を向上することのできる再生ゴム含有ゴム組成物及び空気入りタイヤを得るために、ゴム組成物に、微粒径化処理を施し、２００メッシュのふるいを通過したもののみを実質的に含む粉末ゴムを、更にオイルパン法により処理して得られた再生ゴムを含有させている（例えば、特許文献１参照）。 For example, excellent rubber properties, especially high fracture characteristics, can be secured without sacrificing workability and workability, and the material recycling rate of waste rubber obtained from rubber products such as used tires is improved. In order to obtain a reclaimed rubber-containing rubber composition and a pneumatic tire that can be made, the rubber composition is subjected to a fine particle size treatment, and a powder rubber substantially containing only that passed through a 200-mesh sieve, Furthermore, the recycled rubber obtained by processing by an oil pan method is contained (for example, refer patent document 1).
　また、引張り強度及び耐摩耗性の低下を可及的に小さくするようにした再生ゴム入りタイヤ用ゴム組成物、特にタイヤトレッド用に好適な再生ゴム入りタイヤ用ゴム組成物を得るために、再生ゴムを除くジエン系ゴム１００重量部に対し、再生ゴムを１０～５０重量部配合する場合のカーボンブラック及びオイル成分を、特定の式で求められる配合量で配合することが開示されている（例えば、特許文献２参照）。 In addition, in order to obtain a rubber composition for tires with recycled rubber in which the decrease in tensile strength and wear resistance is made as small as possible, in particular, a rubber composition for tires with recycled rubber suitable for tire treads is recycled. It is disclosed that carbon black and an oil component in the case where 10 to 50 parts by weight of recycled rubber is blended with 100 parts by weight of a diene rubber excluding rubber are blended in a blending amount obtained by a specific formula (for example, , See Patent Document 2).
特開２００７－１２６５１８号公報JP 2007-126518 A 特開２００９－２０９２４０号公報JP 2009-209240 A
　しかし、廃ゴムから得られた再生ゴムは、新ゴムに比べ、ゴムとして求められる諸性能が低下しているため、再生ゴムと新ゴムとを混合して得られるゴム組成物は、再生ゴムの配合量が多いほど性能が低下し易かった。そのため、ゴム製品（例えば、タイヤ）に求められる特性を損なわずに再生ゴムを混合するには、再生ゴムの量を少なくせざるを得ず、特許文献１では、新ゴムの５０質量％未満、特許文献２では多くても新ゴムの５０質量％までしか再生ゴムを用いることができなかった。 However, since the recycled rubber obtained from waste rubber has various performances required as rubber compared to the new rubber, the rubber composition obtained by mixing the recycled rubber and the new rubber is made of recycled rubber. As the blending amount increased, the performance easily decreased. Therefore, in order to mix recycled rubber without impairing the characteristics required for rubber products (for example, tires), the amount of recycled rubber must be reduced. In Patent Document 1, less than 50% by mass of new rubber, In Patent Document 2, the recycled rubber can be used only at most up to 50% by mass of the new rubber.
　また、ゴムがより厳しい環境下で使用される用途に用いられる場合は、タイヤ用ゴムに求められる特性よりも高い特性が求められる。例えば、ブルトーザーのような建築機械は、舗装道路を走行するタイヤと異なり、整備されていない地面を走行することが多く、自動車よりも重い車体である。そのため、ブルトーザー等の走行部を構成するゴムクローラは、タイヤよりも高い引張強度、耐摩耗性等が要求される。 Also, when rubber is used in applications where it is used in a harsher environment, characteristics higher than those required for tire rubber are required. For example, a construction machine such as a bull tozer, unlike a tire traveling on a paved road, often travels on unground ground and is heavier than an automobile. Therefore, a rubber crawler that constitutes a running part such as a bull tozer is required to have higher tensile strength, wear resistance, and the like than a tire.
　本発明は、従来よりも多量の再生ゴムを配合した場合でも引張強度に優れ、かつ耐摩耗性に優れるゴムが得られるゴム組成物及びクローラ用ゴム組成物、並びに、引張強度に優れ、かつ耐摩耗性に優れるラグ部ゴム及びゴムクローラを提供することを目的とする。 The present invention provides a rubber composition and a rubber composition for a crawler that are excellent in tensile strength and excellent in wear resistance even when a larger amount of recycled rubber is blended than before, and excellent in tensile strength and resistance. An object of the present invention is to provide a lug rubber and a rubber crawler excellent in wearability.
＜１＞　ジエン系ゴムを主成分とする未加硫の原料ゴム成分１００質量部と、
　原料ゴム成分１００質量部に対して１００質量部以上５００質量部以下の再生ゴムと、
　（原料ゴム成分１００質量部に対して１．５～２．５質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１．０～３．０質量部）｝となる範囲の加硫剤と、
　（原料ゴム成分１００質量部に対して１．０～３．０質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１．０～４．０質量部）｝となる範囲の酸化亜鉛と、
　（原料ゴム成分１００質量部に対して５０～６０質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１０．０～２０．０質量部）｝となる範囲のカーボンブラックと、
を配合してなるゴム組成物である。
＜２＞　更に、（再生ゴム配合量〔質量部〕／２００）×（０質量部を超え２０．０質量部以下）｝となる範囲のプロセスオイルを配合してなる＜２＞に記載のゴム組成物である。
＜３＞　ジエン系ゴムが、天然ゴム、イソプレンゴム及びスチレンブタジエンゴムからなる群から選ばれる少なくとも一種である＜１＞または＜２＞に記載のゴム組成物。
＜４＞　原料ゴム成分が原料ゴム成分全質量に対し５０質量％以上の天然ゴムを含む＜１＞～＜３＞のいずれか１つに記載のゴム組成物である。
＜５＞　＜１＞～＜４＞のいずれか１つに記載のゴム組成物を含むクローラ用ゴム組成物である。
＜６＞　＜５＞に記載のクローラ用ゴム組成物から得られるラグ部ゴムである。
＜７＞　＜５＞に記載のクローラ用ゴム組成物から得られるゴムクローラである。
＜８＞　＜６＞に記載のラグ部ゴムを備えたゴムクローラである。 <1> 100 parts by mass of an unvulcanized raw rubber component mainly composed of a diene rubber;
100 parts by weight or more and 500 parts by weight or less of recycled rubber with respect to 100 parts by weight of the raw rubber component;
(1.5 to 2.5 parts by mass with respect to 100 parts by mass of raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (1.0 to 3.0 parts by mass)} Vulcanizing agent,
(1.0 to 3.0 parts by mass with respect to 100 parts by mass of raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (1.0 to 4.0 parts by mass)} With zinc oxide,
Carbon black in a range of (50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (10.0 to 20.0 parts by mass)} ,
Is a rubber composition formed by blending
<2> The rubber according to <2>, further comprising a process oil in a range of (recycled rubber compounding amount [parts by mass] / 200) × (exceeding 0 parts by mass and 20.0 parts by mass or less)}. It is a composition.
<3> The rubber composition according to <1> or <2>, wherein the diene rubber is at least one selected from the group consisting of natural rubber, isoprene rubber, and styrene butadiene rubber.
<4> The rubber composition according to any one of <1> to <3>, wherein the raw rubber component includes 50% by mass or more of natural rubber with respect to the total mass of the raw rubber component.
<5> A rubber composition for a crawler comprising the rubber composition according to any one of <1> to <4>.
<6> A rug rubber obtained from the rubber composition for a crawler according to <5>.
<7> A rubber crawler obtained from the rubber composition for a crawler according to <5>.
<8> A rubber crawler provided with the lug rubber described in <6>.
　本発明によれば、従来よりも多量の再生ゴムを配合した場合でも引張強度に優れ、かつ耐摩耗性に優れるゴムが得られるゴム組成物及びクローラ用ゴム組成物、並びに、引張強度に優れ、かつ耐摩耗性に優れるラグ部ゴム及びゴムクローラを提供することができる。 According to the present invention, even when a larger amount of recycled rubber is blended than before, a rubber composition and a rubber composition for a crawler that are excellent in tensile strength and excellent in wear resistance, and excellent in tensile strength, In addition, a lug rubber and a rubber crawler excellent in wear resistance can be provided.
＜ゴム組成物＞
　本発明のゴム組成物は、ジエン系ゴムを主成分とする未加硫の原料ゴム成分１００質量部と、原料ゴム成分１００質量部に対して１００質量部以上５００質量部以下の再生ゴムと、（原料ゴム成分１００質量部に対して１．５～２．５質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１．０～３．０質量部）｝となる範囲の加硫剤と、（原料ゴム成分１００質量部に対して１．０～３．０質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１．０～４．０質量部）｝となる範囲の酸化亜鉛と、（原料ゴム成分１００質量部に対して５０～６０質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１０．０～２０．０質量部）｝となる範囲のカーボンブラックと、を配合してなる。
　本発明のゴム組成物は、更に、プロセスオイル、老化防止剤等の添加剤が配合されていてもよい。
　本発明のゴム組成物が上記構成であることで、ゴム組成物を加硫して得られるゴムが引張強度に優れ、かつ耐摩耗性に優れる理由は定かではないが、次の理由によるものと推察される。 <Rubber composition>
The rubber composition of the present invention comprises 100 parts by mass of an unvulcanized raw rubber component mainly composed of a diene rubber, 100 parts by mass or more and 500 parts by mass or less of a recycled rubber with respect to 100 parts by mass of the raw rubber component, (1.5 to 2.5 parts by mass with respect to 100 parts by mass of raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (1.0 to 3.0 parts by mass)} Vulcanizing agent and (1.0 to 3.0 parts by mass with respect to 100 parts by mass of the raw rubber component) + {(blended amount of recycled rubber [parts by mass] / 200) × (1.0 to 4.0 masses) Parts)} and zinc oxide in the range of (50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (10.0 to 20.0) Carbon black in a range of (parts by mass)}.
The rubber composition of the present invention may further contain additives such as process oil and anti-aging agent.
The reason why the rubber composition obtained by vulcanizing the rubber composition is excellent in tensile strength and wear resistance is not certain because the rubber composition of the present invention has the above-described configuration, but the reason is as follows. Inferred.
　既述のように、新ゴムである未加硫の原料ゴム成分と、再生ゴムとを含む従来のゴム組成物は、再生ゴムの配合量が多いほど、得られるゴムの性能が低下する傾向にある。これは、未加硫の原料ゴム成分と、加硫済みである再生ゴムとを加硫剤等と共に混練して加硫しても、原料ゴム成分と再生ゴムとは、渾然一体とはなりにくく、分離し易いことから、ゴム組成物から得られるゴムの引張強度等の性能が低下すると考えられる。
　ゴム組成物の加硫反応においては、再生ゴムが加硫剤を吸収し易く、原料ゴム成分に比べて再生ゴムの加硫反応が進み易いため、原料ゴム成分の加硫剤の吸収量と、再生ゴムの加硫剤の吸収量とに差が生じ易いと考えられる。その結果、ゴム成分のマトリックスの中で、より加硫が進み硬くなった再生ゴム由来の領域と、加硫があまり進んでいない原料ゴム成分由来の領域とで、界面が生じ易くなると考えられる。そのため、ゴム組成物を加硫して得たゴムに対して、外部から負荷をかけると、再生ゴム由来の領域と原料ゴム成分由来の領域との界面を境に分解ないし破断し易く、ゴムの引張強度等が低下すると考えられる。 As described above, the conventional rubber composition containing the unvulcanized raw rubber component, which is a new rubber, and recycled rubber tends to decrease the performance of the resulting rubber as the amount of recycled rubber increases. is there. This is because even if the unvulcanized raw rubber component and the vulcanized recycled rubber are kneaded and vulcanized together with a vulcanizing agent etc., the raw rubber component and the recycled rubber are not easily integrated. Since it is easy to separate, it is considered that performance such as tensile strength of rubber obtained from the rubber composition is lowered.
In the vulcanization reaction of the rubber composition, the recycled rubber easily absorbs the vulcanizing agent, and the vulcanization reaction of the recycled rubber proceeds more easily than the raw rubber component. It is considered that a difference is likely to occur in the amount of vulcanizing agent absorbed in recycled rubber. As a result, it is considered that in the rubber component matrix, an interface is likely to be generated between the region derived from the regenerated rubber that has been hardened and hardened, and the region derived from the raw rubber component that has not undergone much vulcanization. Therefore, when a load is applied from the outside to the rubber obtained by vulcanizing the rubber composition, it is easily decomposed or broken at the boundary between the region derived from the recycled rubber and the region derived from the raw rubber component. It is thought that tensile strength etc. will fall.
　従来、再生ゴムは、原料ゴム成分と共に添加する充填剤の一種として再生ゴムを添加していたため、未加硫の原料ゴムの加硫が十分に行えなかった。しかしながら、単に、加硫剤、加硫促進剤等を増加するのみではゴムの強度を十分に向上することができず、又は、加硫反応が進みすぎ、ゴムが脆くなった。
　本発明では、理由は定かではないが、ゴム組成物を上記構成とすることで、加硫剤が再生ゴムに移行する前に、原料ゴム成分の加硫を進めることができ、原料ゴム成分の加硫剤の吸収量と、再生ゴムの加硫剤の吸収量との差を小さくすることができると考えられる。その結果、再生ゴム由来のゴムと、原料ゴム成分由来のゴムとが渾然一体に混合し、得られるゴムの引張強度が向上し、耐摩耗性にも優れるものとなると考えられる。
　以下、本発明のゴム組成物の構成について、詳細に説明する。 Conventionally, since recycled rubber has been added as a kind of filler added together with the raw rubber component, the raw rubber has not been sufficiently vulcanized. However, simply increasing the vulcanizing agent, vulcanization accelerator, etc. cannot sufficiently improve the strength of the rubber, or the vulcanization reaction has progressed too much, making the rubber brittle.
In the present invention, the reason is not clear, but by configuring the rubber composition as described above, the raw rubber component can be vulcanized before the vulcanizing agent is transferred to the recycled rubber. It is considered that the difference between the amount of vulcanizing agent absorbed and the amount of recycled rubber vulcanizing agent absorbed can be reduced. As a result, it is considered that the rubber derived from the recycled rubber and the rubber derived from the raw rubber component are mixed together and the resulting rubber has improved tensile strength and excellent wear resistance.
Hereinafter, the structure of the rubber composition of this invention is demonstrated in detail.
〔原料ゴム成分〕
　原料ゴム成分は、ジエン系ゴムを主成分とする未加硫のゴム成分である。
　再生ゴムとして入手し得るゴムは、一般に廃タイヤを原料とするものであるため、再生ゴムとの混合性の観点からジエン系を主成分とする。なお、主成分とは、原料ゴム成分の全質量に対し、７０質量％以上を占める成分をいい、原料ゴム成分は、原料ゴム成分の全質量に対し３０質量％以下を限度に、非ジエン系ゴムを含んでいてもよい。 [Raw rubber component]
The raw rubber component is an unvulcanized rubber component mainly composed of a diene rubber.
Since rubbers that can be obtained as recycled rubber are generally made from waste tires, they are mainly composed of a diene system from the viewpoint of miscibility with recycled rubber. The main component means a component that occupies 70% by mass or more with respect to the total mass of the raw rubber component, and the raw rubber component is a non-diene-based material up to 30% by mass or less with respect to the total mass of the raw rubber component. It may contain rubber.
　ジエン系ゴムとしては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、（ハイシス）ブタジエンゴム［（ハイシス）ＢＲ］、スチレンブタジエンゴム（ＳＢＲ）、エチレン－プロピレンゴム（ＥＰＲ）、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム、クロロプレンゴム又はこれらの混合物（例えば、天然ゴムとスチレンブタジエンゴムとの混合物）などが挙げられる。
　非ジエン系ゴムとしては、ブチルゴム、エチレンプロピレンゴム、ウレタンゴム、シリコーンゴム、アクリルゴムなどが挙げられる。 Diene rubbers include natural rubber (NR), isoprene rubber (IR), (high cis) butadiene rubber [(high cis) BR], styrene butadiene rubber (SBR), ethylene-propylene rubber (EPR), and ethylene-propylene-diene rubber. (EPDM), butyl rubber (IIR), halogenated butyl rubber, chloroprene rubber, or a mixture thereof (for example, a mixture of natural rubber and styrene butadiene rubber).
Non-diene rubbers include butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, acrylic rubber and the like.
　原料ゴム成分は、ジエン系ゴムを８０質量％以上含むことが好ましく、９０質量％以上含むことがより好ましく、９５質量％以上含むことが更に好ましい。更に、ジエン系ゴム全質量に対し、天然ゴムの含有量が、５０質量％以上であることが好ましい。 The raw rubber component preferably contains 80% by mass or more of diene rubber, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Furthermore, it is preferable that the content of natural rubber is 50% by mass or more based on the total mass of the diene rubber.
〔再生ゴム〕
　本発明で使用する再生ゴムは、市販の再生ゴムを使用することができる。再生ゴムとは、ＪＩＳ　Ｋ６３１３－２０１２に規定された自動車用タイヤ、チューブ及びその他のゴム製品の使用済みのゴムなどを再生したもの並びにこれと同等の性状を有するものとする。なお、粉状のものは除く。また、脱硫処理が施された再生ゴムである。
　再生ゴムの種類は、チューブ再生ゴム、タイヤ再生ゴム、その他の再生ゴムから選ばれるいずれでもよく、複数の種類を組み合わせることもできる。これらの中でも、タイヤ再生ゴムが好ましい。再生ゴムは、ジエン系ゴムが主成分（再生ゴムのゴム成分中５０質量％以上）であることが、さらに好ましい。
　再生ゴムの製造方法としては特に限定されず、オイルパン法、リクレメーター法など、公知の方法を採用すればよい。 [Recycled rubber]
Commercially available recycled rubber can be used as the recycled rubber used in the present invention. Recycled rubber is a regenerated rubber used for automobile tires, tubes and other rubber products as defined in JIS K6313-2012, and has the same properties as this. Note that powders are excluded. Further, it is a recycled rubber that has been subjected to desulfurization treatment.
The type of recycled rubber may be any one selected from tube recycled rubber, tire recycled rubber, and other recycled rubber, and a plurality of types may be combined. Among these, tire recycled rubber is preferable. It is more preferable that the recycled rubber is mainly composed of a diene rubber (50% by mass or more in the rubber component of the recycled rubber).
It does not specifically limit as a manufacturing method of a recycled rubber, What is necessary is just to employ | adopt well-known methods, such as an oil pan method and a recremeter method.
　本発明において、再生ゴムは、原料ゴム成分１００質量部に対して１００質量部以上５００質量部以下となる範囲でゴム組成物に配合される。再生ゴムの配合量が原料ゴム成分１００質量部に対して１００質量部未満であると、得られるゴムの物性は低下しにくく、諸機能も維持し易いが、再生ゴムのリサイクル量として不十分であり、従来よりも多量の再生ゴムを使用したことにならない。再生ゴムの配合量が原料ゴム成分１００質量部に対して５００質量部を超えると、ゴムの物性が低下し、ゴムの諸機能を維持することができない。
　再生ゴムの配合量は、再生ゴムのリサイクル量を多くする観点から、原料ゴム成分１００質量部に対して２００質量部以上とすることが好ましく、３００質量部以上とすることがより好ましく、４００質量部以上とすることが更に好ましい。 In the present invention, the recycled rubber is blended in the rubber composition in a range of 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the raw rubber component. When the amount of the recycled rubber is less than 100 parts by mass with respect to 100 parts by mass of the raw rubber component, the physical properties of the resulting rubber are difficult to deteriorate and various functions are easily maintained, but the recycled amount of the recycled rubber is insufficient. Yes, a larger amount of recycled rubber is not used than before. When the amount of the recycled rubber exceeds 500 parts by mass with respect to 100 parts by mass of the raw rubber component, the physical properties of the rubber are lowered and the various functions of the rubber cannot be maintained.
From the viewpoint of increasing the amount of recycled rubber recycled, the amount of recycled rubber is preferably 200 parts by mass or more, more preferably 300 parts by mass or more, and 400 parts by mass with respect to 100 parts by mass of the raw rubber component. More preferably, it is more than part.
〔加硫剤〕
　加硫剤は、本発明のゴム組成物に、原料ゴム成分１００質量部に対して１．５～２．５質量部となる基礎配合に対し、更に、｛（再生ゴム配合量〔質量部〕／２００）×（１．０～３．０質量部）｝となる範囲で追加配合される。
　加硫剤の基礎配合量は、原料ゴム成分の加硫を十分に行う観点から、１．７～２．３質量部であることが好ましい。
　加硫剤の追加配合量は、耐摩耗性を向上する観点から、１．２～３．０質量部であることが好ましい。
　加硫剤は、硫黄、又は、硫黄を含有する化合物であれば、特に制限されない。 [Vulcanizing agent]
The vulcanizing agent is added to the rubber composition of the present invention in a basic compounding amount of 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the raw rubber component, and {(recycled rubber compounding amount [parts by mass]]. /200)×(1.0 to 3.0 parts by mass)}.
The basic compounding amount of the vulcanizing agent is preferably 1.7 to 2.3 parts by mass from the viewpoint of sufficiently vulcanizing the raw rubber component.
The added amount of the vulcanizing agent is preferably 1.2 to 3.0 parts by mass from the viewpoint of improving the wear resistance.
The vulcanizing agent is not particularly limited as long as it is sulfur or a compound containing sulfur.
〔酸化亜鉛〕
　酸化亜鉛は、本発明のゴム組成物に、原料ゴム成分１００質量部に対して１．０～３．０質量部となる基礎配合に対し、更に、｛（再生ゴム配合量〔質量部〕／２００）×（１．０～４．０質量部）｝となる範囲で追加配合される。
　酸化亜鉛の基礎配合量は、原料ゴム成分の加硫を十分に行う観点から、２．０～３．０質量部であることが好ましい。
　酸化亜鉛の追加配合量は、原料ゴム成分の加硫を効率的に行ない、再生ゴムの加硫剤吸収量と、原料ゴム成分の加硫剤吸収量との差を小さくする観点から、１．２～４．０質量部であることが好ましい。 [Zinc oxide]
Zinc oxide is added to the rubber composition of the present invention in the basis of 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the raw rubber component, and {(recycled rubber compounding amount [parts by mass] / 200) × (1.0 to 4.0 parts by mass)}.
The basic compounding amount of zinc oxide is preferably 2.0 to 3.0 parts by mass from the viewpoint of sufficiently vulcanizing the raw rubber component.
From the viewpoint of efficiently vulcanizing the raw rubber component and reducing the difference between the vulcanizing agent absorption amount of the recycled rubber and the vulcanizing agent absorption amount of the raw rubber component, 1. The amount is preferably 2 to 4.0 parts by mass.
〔加硫促進剤〕
　加硫促進剤は、本発明のゴム組成物に、原料ゴム成分１００質量部に対して０．４～１．０質量部となる基礎配合に対し、更に、｛（再生ゴム配合量〔質量部〕／２００）×（０．１～１．０質量部）｝となる範囲で追加配合されることが好ましい。
　ゴム組成物の加硫時の作業性の観点から、加硫促進剤の基礎配合量は、原料ゴム成分１００質量部に対して０．４～０．８質量部が好ましく、追加配合量は（再生ゴム配合量〔質量部〕／２００）×（０．４～０．９質量部）｝であることが好ましい。
　加硫促進剤は、特に限定されるものではないが、例えば、Ｍ（２－メルカプトベンゾチアゾール）、ＤＭ（ジベンゾチアジルジスルフィド）、ＣＺ（Ｎ－シクロヘキシル－２－ベンゾチアジルスルフェンアミド）等のチアゾール系、あるいはＤＰＧ（ジフェニルグアニジン）等のグアニジン系の加硫促進剤等を挙げることができる。 [Vulcanization accelerator]
The vulcanization accelerator is added to the rubber composition of the present invention in a basic compounding amount of 0.4 to 1.0 part by mass with respect to 100 parts by mass of the raw rubber component. ] / 200) × (0.1 to 1.0 part by mass)} is preferably added.
From the viewpoint of workability during vulcanization of the rubber composition, the basic compounding amount of the vulcanization accelerator is preferably 0.4 to 0.8 parts by mass with respect to 100 parts by mass of the raw rubber component, and the additional compounding amount is ( The amount of recycled rubber [parts by mass] / 200) × (0.4 to 0.9 parts by mass)} is preferred.
The vulcanization accelerator is not particularly limited. For example, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. And guanidine vulcanization accelerators such as DPG (diphenylguanidine).
〔カーボンブラック〕
　カーボンブラックは、本発明のゴム組成物に、原料ゴム成分１００質量部に対して５０～６０質量部となる基礎配合に対し、更に、｛（再生ゴム配合量〔質量部〕／２００）×（１０．０～２０．０質量部）｝となる範囲で追加配合される。
　カーボンブラックの基礎配合量は、原料ゴム成分の加硫を効率的に行ない、再生ゴムの加硫剤吸収量と、原料ゴム成分の加硫剤吸収量との差を小さくする観点から、５５～６０質量部であることが好ましい。
　カーボンブラックの追加配合量は、加硫ゴムの破断強度の観点から、１２．０～２０．０質量部であることが好ましい。加硫ゴムの引き裂き強度の観点からは、１０．０～１８．０質量部であることが好ましい。
　カーボンブラックとしては、標準品種であるＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦ、ＧＰＦ、ＳＲＦ（以上ゴム用ファーネス）、ＭＴカーボンブラック（熱分解カーボン）などを挙げることができる。 〔Carbon black〕
Carbon black is added to the rubber composition of the present invention in addition to the basic compounding amount of 50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component, {(recycled rubber compounding amount [parts by mass] / 200) × ( (10.0 to 20.0 parts by mass)}.
The basic compounding amount of carbon black is 55 to 50% from the viewpoint of efficiently vulcanizing the raw rubber component and reducing the difference between the vulcanizing agent absorption amount of the recycled rubber and the vulcanizing agent absorption amount of the raw rubber component. The amount is preferably 60 parts by mass.
The additional amount of carbon black is preferably 12.0 to 20.0 parts by mass from the viewpoint of the breaking strength of the vulcanized rubber. From the viewpoint of the tear strength of the vulcanized rubber, the amount is preferably 10.0 to 18.0 parts by mass.
Examples of carbon black include standard varieties such as SAF, ISAF, HAF, FEF, GPF, SRF (furnace for rubber) and MT carbon black (pyrolytic carbon).
〔プロセスオイル〕
　プロセスオイルは、本発明のゴム組成物に、更に、｛（再生ゴム配合量〔質量部〕／２００）×（０質量部を超え２０．０質量部以下）｝となる範囲で追加配合してもよい。
　プロセスオイルが配合されることで、ゴム組成物を混練する際の作業性を向上することができる。
　プロセスオイルの追加配合量は、ゴム組成物の混練時の作業性を向上しつつ、ゴムの可塑化を抑制する観点から、５．０～１５．０質量部であることが好ましい。
　プロセスオイルとしては、例えばパラフィン系、ナフテン系、アロマチック系のプロセスオイルを挙げることができる。 [Process oil]
The process oil is further added to the rubber composition of the present invention in the range of {(recycled rubber compounding amount [parts by mass] / 200) × (exceeding 0 parts by mass and 20.0 parts by mass or less)}. Also good.
By blending the process oil, workability when kneading the rubber composition can be improved.
The additional amount of the process oil is preferably 5.0 to 15.0 parts by mass from the viewpoint of suppressing rubber plasticization while improving workability during kneading of the rubber composition.
Examples of the process oil include paraffinic, naphthenic, and aromatic process oils.
　本発明のゴム組成物には、本発明の目的が損なわれない範囲で、更に他の添加剤を含有させてもよい。かかる添加剤としては、通常、ゴムに含有されるものであれば特に制限は無いが、例えば、ステアリン酸などの脂肪酸；樹脂；老化防止剤；ワックス；加硫遅延剤（スコーチ防止剤）；シリカ；シリカカップリング剤；しゃく解剤；オゾン亀裂防止剤；抗酸化剤；クレー；炭酸カルシウム等が挙げられる。これらは、市販品を使用できる。添加剤の添加量は、本発明の目的が損なわれない範囲で当業者が適宜選択できる。 The rubber composition of the present invention may further contain other additives as long as the object of the present invention is not impaired. Such additives are not particularly limited as long as they are usually contained in rubber. For example, fatty acids such as stearic acid; resins; anti-aging agents; waxes; vulcanization retarders (scorching inhibitors); Silica coupling agent; peptizer; ozone cracking inhibitor; antioxidant; clay; calcium carbonate. A commercial item can be used for these. The amount of the additive added can be appropriately selected by those skilled in the art as long as the object of the present invention is not impaired.
　脂肪酸を使用する場合、その配合量は、原料ゴム成分１００質量部に対し、０．１～５質量部が好ましく、０．５～３質量部がより好ましい。 When using a fatty acid, the blending amount is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the raw rubber component.
　樹脂としては、ポリエステルポリオール樹脂、ジシクロペンタジエン樹脂、ロジン樹脂、フェノール樹脂、キシレン樹脂、脂肪・脂環族Ｃ５系石油樹脂、Ｃ５／Ｃ９系石油樹脂、Ｃ９系石油樹脂、テルペン樹脂、並びにこれらの共重合体及び変性品などを挙げることができる。樹脂を使用する場合、その配合量は、原料ゴム成分１００質量部に対し、０．５～２０質量部であることが好ましく、１～１０質量部であることがより好ましい。 Examples of the resin include polyester polyol resin, dicyclopentadiene resin, rosin resin, phenol resin, xylene resin, aliphatic / alicyclic C5 petroleum resin, C5 / C9 petroleum resin, C9 petroleum resin, terpene resin, and these Examples include copolymers and modified products. When the resin is used, the amount of the resin is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the raw rubber component.
　老化防止剤としては、公知の老化防止剤を選択し用いることができる。例えば、Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン（６Ｃ）、Ｎ－フェニル－Ｎ’－イソプロピル－ｐ－フェニレンジアミン（３Ｃ）、２，２，４－トリメチル－１，２－ジヒドロキノリン重合物（ＲＤ）などが挙げられる。老化防止剤を使用する場合、その配合量は、原料ゴム成分１００質量部に対し、０．５～１０質量部が好ましい。 As the anti-aging agent, a known anti-aging agent can be selected and used. For example, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (6C), N-phenyl-N′-isopropyl-p-phenylenediamine (3C), 2,2,4-trimethyl -1,2-dihydroquinoline polymer (RD) and the like. When an anti-aging agent is used, its blending amount is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the raw rubber component.
　ワックスを使用する場合、その配合量は、原料ゴム成分１００質量部に対し、０．５～１０質量部が好ましく、１～５質量部がより好ましい。 When using wax, the blending amount is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the raw rubber component.
＜ゴム組成物の製造方法＞
　このように、本発明のゴム組成物は、既述の成分を混練することにより得られる。混練方法は、当業者が通常実施する方法に従えばよく、例えば、硫黄、加硫促進剤、及び酸化亜鉛以外の全成分（加硫遅延剤を用いる場合は、更に、加硫遅延剤を含む）を、バンバリーミキサー、ブラベンダー、ニーダー、高剪断型ミキサーなどを用いて１００～２００℃で混練した後、硫黄、加硫促進剤、及び酸化亜鉛（必要に応じて、更に加硫遅延剤）を添加して、混練ロール機などで６０～１３０℃で混練すればよい。 <Method for producing rubber composition>
Thus, the rubber composition of the present invention can be obtained by kneading the aforementioned components. The kneading method may be in accordance with a method usually carried out by those skilled in the art. For example, all components other than sulfur, a vulcanization accelerator, and zinc oxide (when a vulcanization retarder is used, a vulcanization retarder is further included). ) Using a Banbury mixer, Brabender, kneader, high shear mixer, etc., and then kneaded at 100 to 200 ° C., and then sulfur, vulcanization accelerator, and zinc oxide (additional vulcanization retarder if necessary) And kneading at 60 to 130 ° C. with a kneading roll machine or the like.
＜クローラ用ゴム組成物、ラグ部ゴム、及びゴムクローラ＞
　本発明のゴム組成物は、加硫により得られるゴムが引張強度及び耐摩耗性に優れるため、クローラ用ゴム組成物に適している。
　本発明のゴム組成物又はクローラ用ゴム組成物を加熱金型によって成形することにより、引張強度及び耐摩耗性に優れるゴムを得ることができ、加熱金型を変えることで、所望のゴムクローラ及びゴムクローラのラグ部ゴムを得ることができる。 <Crawler rubber composition, lug rubber, and rubber crawler>
The rubber composition of the present invention is suitable for a rubber composition for crawlers because a rubber obtained by vulcanization is excellent in tensile strength and wear resistance.
By molding the rubber composition of the present invention or the rubber composition for a crawler with a heating mold, it is possible to obtain a rubber having excellent tensile strength and wear resistance. By changing the heating mold, a desired rubber crawler and A rubber crawler lug rubber can be obtained.
　次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。なお、各分析は以下の通りに行なった。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Each analysis was performed as follows.
＜実施例１～１１及び比較例１～６＞
　表１及び表２に示した配合（単位：質量部）で、硫黄及び加硫促進剤を除く各成分をバンバリーミキサーにて１５０℃で混練し、引き続き硫黄及び加硫促進剤を添加して混練することによりゴム組成物を得、該ゴム組成物を金型温度１５０℃で成形することによりゴムクローラを得た。
　得られたゴム組成物の作業性及びゴムクローラの引張強度および耐摩耗性を以下のようにして測定し、結果を表１及び表２に示した。
　なお、ゴムクローラの引張強度および耐摩耗性は、ゴム組成物を、ゴムクローラの製造条件と同じ金型温度１５０℃で成形することにより得た試験片を用いて評価した。 <Examples 1 to 11 and Comparative Examples 1 to 6>
In the composition shown in Table 1 and Table 2 (unit: parts by mass), each component excluding sulfur and vulcanization accelerator is kneaded at 150 ° C. with a Banbury mixer, and then sulfur and vulcanization accelerator are added and kneaded. Thus, a rubber composition was obtained, and the rubber composition was molded at a mold temperature of 150 ° C. to obtain a rubber crawler.
The workability of the obtained rubber composition and the tensile strength and wear resistance of the rubber crawler were measured as follows, and the results are shown in Tables 1 and 2.
The tensile strength and wear resistance of the rubber crawler were evaluated using a test piece obtained by molding the rubber composition at a mold temperature of 150 ° C., which is the same as the rubber crawler production conditions.
〔混練り作業性〕
　ゴム組成物の混練時の様子を目し観察し、下記評価基準により評価した。
Ａ：ゴム組成物がよくまとまり、バンバリーミキサーにへばりつく様子も見られなかった。
Ｂ：ゴム組成物がまとまらずに砕けて零れ落ちる様子、バンバリーミキサーにへばりつく様子、又はその両方の様子が見られた。 [Kneading workability]
The rubber composition was observed while being kneaded and evaluated according to the following evaluation criteria.
A: The rubber composition was well organized, and no clinging to the Banbury mixer was observed.
B: A state in which the rubber composition was crushed and spilled without being settled, clinged to a Banbury mixer, or both were observed.
〔引張強度（Ｔｂ、トラウザ引裂）〕
（Ｔｂ）
　得られた試験片を、ダンベル状３号形のダンベル状試験片（ＪＩＳ　Ｋ６２９９（２０１２））の形状に切り出した。得られたダンベル状試験片を、ＪＩＳ　Ｋ６２５１（２０１０）に準じて、引張り試験装置を用いて、２５℃で、規定速度（５００±２５ｍｍ／ｍｉｎ）で破断するまで引っ張り、破断させるのに要した最大の引張り力を引張破断強度（Ｔｂ：Ｔｅｎｓｉｌｅ　Ｓｔｒｅｎｇｔｈ　ａｔ　ｂｒｅａｋ）とした。表１及び表２には、比較例２の引張破談強度を１００％として指数表示した。指数値が大きいほど、引張破断強度が大きいことを示す。指数値は１２０％以上を許容範囲とし、１３０％以上であることが好ましい。 [Tensile strength (Tb, Trouser tear)]
(Tb)
The obtained test piece was cut into the shape of a dumbbell-shaped No. 3 dumbbell-shaped test piece (JIS K6299 (2012)). The obtained dumbbell-shaped test piece was required to be pulled and broken at 25 ° C. at a specified speed (500 ± 25 mm / min) using a tensile test device in accordance with JIS K6251 (2010). The maximum tensile force was taken as the tensile strength at break (Tb). In Tables 1 and 2, the tensile breaking strength of Comparative Example 2 is shown as an index with 100%. A larger index value indicates a higher tensile rupture strength. The allowable index value is 120% or more, preferably 130% or more.
（トラウザ引裂）
　トラウザ形引裂き試験［ＪＩＳ　Ｋ６２５２（１９９３）］に準拠して、試験片を厚さ２ｍｍのトラウザ型試験片に切り出し、２５℃で引裂き力を測定した。比較例２の引裂き力を１００％として指数表示した。指数値が大きいほど、引き裂きにくいことを示す。指数値は９０％以上を許容範囲とする。 (Trouser tear)
In accordance with a trouser-type tear test [JIS K6252 (1993)], a test piece was cut into a 2 mm-thick trouser-type test piece, and the tearing force was measured at 25 ° C. The tear strength of Comparative Example 2 was taken as 100% and displayed as an index. It shows that it is hard to tear, so that an index value is large. The allowable index value is 90% or more.
〔耐摩耗性（製品摩耗速度）〕
　ランボーン型摩耗試験機を使用して、２５℃における試験片の製品摩耗速度〔ｍｍ／１００ｈｒ〕を測定した。製品摩耗速度が比較例２の製品摩耗速度より小さいほど、摩耗しにくいことを表し、耐摩耗性に優れることを示す。製品摩耗速度は２．５以下を許容範囲とする。 [Abrasion resistance (product wear rate)]
The product wear rate [mm / 100 hr] of the test piece at 25 ° C. was measured using a Lambbone type wear tester. The smaller the product wear rate than the product wear rate of Comparative Example 2, the harder it is to wear and the better the wear resistance. The product wear rate should be 2.5 or less.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び表２の各成分の詳細は次のとおりである。
１）天然ゴム：グレード；ＴＳＲ２０号
２）ＳＢＲ１５００：ＴＡＩＰＯＬ１５００Ｅ（商品名）、スチレンブタジエンゴム、ＴＳＲＣ社製
３）再生ゴム：タイヤ再生ゴム、村岡ゴム工業株式会社製
４）カーボンブラック：旭♯７０（商品名）、旭カーボン株式会社製
５）ステアリン酸：ＰＡＬＭＡＣ１６００（商品名）、ＡＣＩＤＣＨＥＭ社製
６）ワックス：パラフィンワックス１３５（商品名）、日本精鑞株式会社製
７）老化防止剤　ＲＤ：「ノクラック（登録商標）２２４」（商品名）、大内新興化学工業株式会社製
８）老化防止剤　６Ｃ：「ＡＮＴＩＧＥＮＥ（登録商標）６Ｃ」（商品名）、住友化学株式会社製
９）オイル：「コウモレックス（登録商標）ＮＨ－６０Ｔ」（商品名）、新日本石油株式会社製
１０）普通硫黄（加硫剤）：Ｓｕｌｆａｘ５（商品名）、鶴見化学工業株式会社製
１１）加硫促進剤　ＤＰＧ：「ノクセラー（登録商標）Ｄ」（商品名）、１，３－ジフェニルグアニジン、大内新興化学工業株式会社製
１２）加硫促進剤　ＣＺ：「ノクセラー（登録商標）ＣＺ－Ｇ」（商品名）、Ｎ－シクロヘキシル－２－ベンゾチアゾリルスルフェンアミド、大内新興化学工業株式会社製
１３）酸化亜鉛：「銀嶺（登録商標）ＳＲ」（商品名）、東邦亜鉛株式会社製
１４）加硫遅延剤　ＰＶＩ：モンサント製、サントガードＰＶＩ（Ｎ－シクロヘキシルチオフタルイミド） The detail of each component of Table 1 and Table 2 is as follows.
1) Natural rubber: Grade; TSR 20 No. 2) SBR 1500: TAIPOL 1500E (trade name), styrene butadiene rubber, manufactured by TSRC 3) Recycled rubber: Tire recycled rubber, manufactured by Muraoka Rubber Co., Ltd. 4) Carbon black: Asahi # 70 ( 5) Stearic acid: PALMAC 1600 (trade name), ACIDCHEM 6) Wax: Paraffin wax 135 (trade name), Nippon Seiki Co., Ltd. 7) Anti-aging agent RD: “NOCRACK” (Registered trademark) 224 "(trade name), manufactured by Ouchi Shinsei Chemical Co., Ltd. 8) Anti-aging agent 6C:" ANTIGENE (registered trademark) 6C "(trade name), manufactured by Sumitomo Chemical Co., Ltd. 9) Oil:" Kou Molex (registered trademark) NH-60T "(trade name), Nippon Oil Corporation 10) Ordinary sulfur (vulcanizing agent) Sulfax5 (trade name), manufactured by Tsurumi Chemical Co., Ltd. 11) Vulcanization accelerator DPG: “Noxeller (registered trademark) D” (trade name), 1,3-diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd. 12) Vulcanization accelerator CZ: “Noxeller (registered trademark) CZ-G” (trade name), N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd. 13) Zinc oxide: (Registered trademark) SR ”(trade name), manufactured by Toho Zinc Co., Ltd. 14) Vulcanization retarder PVI: manufactured by Monsanto, Santguard PVI (N-cyclohexylthiophthalimide)
　表１及び表２からわかるように、実施例では、従来よりも多くの再生ゴムが配合されていても、引張強度及び耐摩耗性に優れた。実施例８のように、原料ゴム１００質量部の５倍となる量を配合しても、引張強度及び耐摩耗性に優れた。
　一方、比較例１及び２からわかるように、再生ゴムを多く含んでも、従来のゴム組成物のような成分構成であると、十分な破断強度が得られなかった。比較例３～５からわかるように、カーボンブラック、加硫剤、及び加硫促進剤を本発明の範囲内で配合しても、それのみでは、耐摩耗性を向上することができなかった。比較例６のように再生ゴムの配合量が多すぎると、ゴム組成物の混練中にゴム組成物がバンバリーミキサーに張り付き、十分な混練をすることができず、作業性が低下し、更には、十分な引張強度が摩耗し易かった。 As can be seen from Tables 1 and 2, in Examples, even when more recycled rubber was blended than in the past, the tensile strength and wear resistance were excellent. As in Example 8, the tensile strength and wear resistance were excellent even when blended in an amount 5 times that of 100 parts by mass of the raw rubber.
On the other hand, as can be seen from Comparative Examples 1 and 2, even when a large amount of recycled rubber was included, a sufficient breaking strength could not be obtained with the component constitution as in the conventional rubber composition. As can be seen from Comparative Examples 3 to 5, even when carbon black, a vulcanizing agent, and a vulcanization accelerator were blended within the scope of the present invention, the wear resistance alone could not be improved. If the amount of recycled rubber is too large as in Comparative Example 6, the rubber composition will stick to the Banbury mixer during kneading of the rubber composition, and sufficient kneading cannot be performed, resulting in reduced workability. Sufficient tensile strength was easy to wear.
　本発明のゴム組成物は、ゴムクローラ及びゴムクローラのラグ部ゴム用途に利用可能である。かかるゴムクローラ又はラグ部ゴムを備えたゴムクローラは、農業機械用、建設機械用又は土木作業機械用に利用可能である。
  The rubber composition of the present invention can be used for rubber crawlers and rubber crawler lug rubber applications. Such a rubber crawler or a rubber crawler provided with a lug rubber can be used for agricultural machinery, construction machinery, or civil engineering machinery.

Claims (8)

  1. 　ジエン系ゴムを主成分とする未加硫の原料ゴム成分１００質量部と、
    　原料ゴム成分１００質量部に対して１００質量部以上５００質量部以下の再生ゴムと、
    　（原料ゴム成分１００質量部に対して１．５～２．５質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１．０～３．０質量部）｝となる範囲の加硫剤と、
    　（原料ゴム成分１００質量部に対して１．０～３．０質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１．０～４．０質量部）｝となる範囲の酸化亜鉛と、
    　（原料ゴム成分１００質量部に対して５０～６０質量部）＋｛（再生ゴム配合量〔質量部〕／２００）×（１０．０～２０．０質量部）｝となる範囲のカーボンブラックと、
    を配合してなるゴム組成物。     100 parts by mass of an unvulcanized raw rubber component mainly composed of a diene rubber;
    100 parts by weight or more and 500 parts by weight or less of recycled rubber with respect to 100 parts by weight of the raw rubber component;
    (1.5 to 2.5 parts by mass with respect to 100 parts by mass of raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (1.0 to 3.0 parts by mass)} Vulcanizing agent,
    (1.0 to 3.0 parts by mass with respect to 100 parts by mass of raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (1.0 to 4.0 parts by mass)} With zinc oxide,
    Carbon black in a range of (50 to 60 parts by mass with respect to 100 parts by mass of the raw rubber component) + {(recycled rubber compounding amount [parts by mass] / 200) × (10.0 to 20.0 parts by mass)} ,
    A rubber composition obtained by blending.
  2. 　更に、（再生ゴム配合量〔質量部〕／２００）×（０質量部を超え２０．０質量部以下）となる範囲のプロセスオイルを配合してなる請求項１に記載のゴム組成物。 The rubber composition according to claim 1, further comprising a process oil in a range of (recycled rubber compounding amount [parts by mass] / 200) × (exceeding 0 parts by mass and 20.0 parts by mass or less).
  3. 　ジエン系ゴムが、天然ゴム、イソプレンゴム及びスチレンブタジエンゴムからなる群から選ばれる少なくとも一種である請求項１または２に記載のゴム組成物。 The rubber composition according to claim 1 or 2, wherein the diene rubber is at least one selected from the group consisting of natural rubber, isoprene rubber and styrene butadiene rubber.
  4. 　原料ゴム成分が原料ゴム成分全質量に対し５０質量％以上の天然ゴムを含む請求項１～３のいずれか１項に記載のゴム組成物。 The rubber composition according to any one of claims 1 to 3, wherein the raw rubber component contains 50% by mass or more of natural rubber with respect to the total mass of the raw rubber component.
  5. 　請求項１～４のいずれか１項に記載のゴム組成物を含むクローラ用ゴム組成物。 A rubber composition for a crawler comprising the rubber composition according to any one of claims 1 to 4.
  6. 　請求項５に記載のクローラ用ゴム組成物から得られるラグ部ゴム。 A lug rubber obtained from the rubber composition for a crawler according to claim 5.
  7. 　請求項５に記載のクローラ用ゴム組成物から得られるゴムクローラ。 A rubber crawler obtained from the rubber composition for crawlers according to claim 5.
  8. 　請求項６に記載のラグ部ゴムを備えたゴムクローラ。
     
     
          A rubber crawler comprising the lug rubber according to claim 6.


PCT/JP2016/087296 2016-01-07 2016-12-14 Rubber composition, rubber composition for crawlers, lug part rubber, and rubber crawler WO2017119254A1 (en)

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CN108945131A (en) * 2018-09-11 2018-12-07 浙江元创橡胶履带有限公司 High speed rubber belt track and high speed rubber belt track decorative pattern side rubber

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JPH1053171A (en) * 1996-08-07 1998-02-24 Bridgestone Corp Rubber crawler
JPH11139359A (en) * 1997-11-04 1999-05-25 Bridgestone Corp Rubber crawler
JP2002265685A (en) * 2001-03-14 2002-09-18 Ube Ind Ltd Rubber composition for passenger car tire
JP2002265680A (en) * 2001-03-15 2002-09-18 Ube Ind Ltd High hardness compounded rubber composition
JP2008056028A (en) * 2006-08-30 2008-03-13 Bridgestone Corp Rubber composition for rubber crawler and rubber crawler
WO2009093695A1 (en) * 2008-01-23 2009-07-30 Ube Industries, Ltd. Rubber composition, rubber composition for base tread, rubber composition for chafer, rubber composition for sidewall, and tire using the rubber compositions
JP2010065138A (en) * 2008-09-10 2010-03-25 Yokohama Rubber Co Ltd:The Rubber composition for tire tread

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