JP5172120B2 - Predetermined cord coating rubber composition and tire having carcass and / or belt using the same - Google Patents
Predetermined cord coating rubber composition and tire having carcass and / or belt using the same Download PDFInfo
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- JP5172120B2 JP5172120B2 JP2006246815A JP2006246815A JP5172120B2 JP 5172120 B2 JP5172120 B2 JP 5172120B2 JP 2006246815 A JP2006246815 A JP 2006246815A JP 2006246815 A JP2006246815 A JP 2006246815A JP 5172120 B2 JP5172120 B2 JP 5172120B2
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Description
本発明は、所定のコード被覆用ゴム組成物ならびにそれを用いたカーカスおよび／またはベルトを有するタイヤに関する。 The present invention relates to a predetermined cord coating rubber composition and a tire having a carcass and / or belt using the same.
一般に、自動車用タイヤには大きな荷重がかかるため、補強材としてコードが用いられている。とくに走行中に、タイヤが発熱することによって、ゴムとコードとが剥離すると、致命的なタイヤ故障の原因となる。 Generally, since a large load is applied to an automobile tire, a cord is used as a reinforcing material. In particular, when the tires generate heat during running and the rubber and cord peel off, a fatal tire failure may occur.
従来、コードには、様々な材料が使用されており、コード被覆用ゴム組成物には、接着性を向上させるために、酸化亜鉛を多量に配合する手法（たとえば、特許文献１参照）が知られている。しかし、酸化亜鉛を多量に配合すると、耐亀裂成長性が悪化するという問題がある。 Conventionally, various materials have been used for the cord, and a method of blending a large amount of zinc oxide with the rubber composition for covering the cord in order to improve adhesiveness (for example, see Patent Document 1) is known. It has been. However, when a large amount of zinc oxide is blended, there is a problem that crack growth resistance deteriorates.
本発明は、所定のコードとの接着性および耐亀裂成長性をともに向上させることができる所定のコード被覆用ゴム組成物、ならびにそれを用いたカーカスおよび／またはベルトを有するタイヤに関する。 The present invention relates to a predetermined cord coating rubber composition capable of improving both adhesion to a predetermined cord and crack growth resistance, and a tire having a carcass and / or belt using the same.
本発明は、ゴム成分１００重量部に対して、平均粒子径が２００ｎｍ以下である超微粒子酸化亜鉛を１〜７重量部配合するポリエステルコード、ナイロンコード、アラミドコードまたはポリエチレンナフタレートコードを被覆するためのコード被覆用ゴム組成物に関する。 The present invention covers a polyester cord, nylon cord, aramid cord or polyethylene naphthalate cord containing 1 to 7 parts by weight of ultrafine zinc oxide having an average particle diameter of 200 nm or less per 100 parts by weight of a rubber component. This invention relates to a rubber composition for covering a cord.
また、本発明は、前記コード被覆用ゴム組成物を用いたカーカスおよび／またはベルトを有するタイヤに関する。 The present invention also relates to a tire having a carcass and / or belt using the rubber composition for covering a cord.
本発明によれば、ゴム成分および所定の超微粒子酸化亜鉛を所定量配合することで、所定のコードとの接着性および耐亀裂成長性をともに向上させることができる所定のコード被覆用ゴム組成物、ならびにそれを用いたカーカスおよび／またはベルトを有するタイヤを提供することができる。 According to the present invention, a predetermined cord coating rubber composition capable of improving both adhesion to a predetermined cord and crack growth resistance by blending a predetermined amount of a rubber component and a predetermined ultrafine zinc oxide. And a tire having a carcass and / or a belt using the same.
本発明のコード被覆用ゴム組成物は、ゴム成分および超微粒子酸化亜鉛を配合する。 The rubber composition for covering a cord of the present invention contains a rubber component and ultrafine zinc oxide.
前記ゴム成分としてはとくに制限はなく、たとえば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、エチレンプロピレンジエンゴム（ＥＰＤＭ）などがあげられ、これらのゴム成分は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。なかでも、コードとの接着性および加硫時の熱安定性の観点から、ＮＲおよびＳＢＲが好ましい。 The rubber component is not particularly limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), ethylene propylene diene rubber (EPDM) These rubber components may be used alone or in combination of two or more. Of these, NR and SBR are preferred from the viewpoints of adhesiveness to the cord and thermal stability during vulcanization.
ＮＲとしては、従来ゴム工業で使用されるＲＳＳ♯３、ＴＳＲ２０などのグレードのＮＲを用いることができる。 As NR, grade NR such as RSS # 3, TSR20 and the like conventionally used in the rubber industry can be used.
本発明で使用する超微粒子酸化亜鉛は、通常使用される酸化亜鉛よりも、平均粒子径の小さいものである。超微粒子酸化亜鉛を配合することで、接着性を向上させつつ、耐亀裂成長性も向上させることが可能となる。 The ultrafine zinc oxide used in the present invention has an average particle size smaller than that of normally used zinc oxide. By blending ultrafine zinc oxide, it is possible to improve the crack growth resistance while improving the adhesion.
超微粒子酸化亜鉛の平均粒子径は２００ｎｍ以下、好ましくは１６０ｎｍ以下である。超微粒子酸化亜鉛の平均粒子径が２００ｎｍをこえると、耐亀裂成長性の低下がみられる場合がある。また、超微粒子酸化亜鉛の平均粒子径は３０ｎｍ以上が好ましく、６０ｎｍ以上がより好ましい。超微粒子酸化亜鉛の平均粒子径が３０ｎｍ未満では、凝集力が非常に強くなり、耐亀裂成長性の改善効果がみられない傾向がある。 The average particle diameter of the ultrafine zinc oxide is 200 nm or less, preferably 160 nm or less. If the average particle diameter of the ultrafine zinc oxide exceeds 200 nm, the crack growth resistance may be lowered. The average particle diameter of the ultrafine zinc oxide is preferably 30 nm or more, and more preferably 60 nm or more. When the average particle diameter of the ultrafine zinc oxide is less than 30 nm, the cohesive force becomes very strong, and there is a tendency that the effect of improving crack growth resistance is not observed.
超微粒子酸化亜鉛の配合量は、ゴム成分１００重量部に対して１重量部以上、好ましくは３重量部以上である。超微粒子酸化亜鉛の配合量が１重量部未満では、超微粒子酸化亜鉛を配合することによる接着性の改善効果が得られない。また、超微粒子酸化亜鉛の配合量は７重量部以下である。超微粒子酸化亜鉛の配合量が７重量部をこえると、分散が困難になり（凝集塊が発生し）、耐亀裂成長性が悪化する。 The blending amount of the ultrafine zinc oxide is 1 part by weight or more, preferably 3 parts by weight or more with respect to 100 parts by weight of the rubber component. When the blending amount of the ultrafine zinc oxide is less than 1 part by weight, the effect of improving the adhesiveness by blending the ultrafine zinc oxide cannot be obtained. The blending amount of ultrafine zinc oxide is 7 parts by weight or less. When the blending amount of the ultrafine zinc oxide exceeds 7 parts by weight, dispersion becomes difficult (agglomerates are generated), and crack growth resistance deteriorates.
本発明のコード被覆用ゴム組成物には、カーボンブラックを配合することが好ましい。 The cord coating rubber composition of the present invention preferably contains carbon black.
カーボンブラックの配合量は、ゴム成分１００重量部に対して３０重量部以上が好ましく、４０重量部以上がより好ましい。カーボンブラックの配合量が３０重量部未満では、ゴム自身の補強性が不充分となり、引張強度が低下する傾向がある。また、カーボンブラックの配合量は１００重量部以下が好ましく、７０重量部以下がより好ましい。カーボンブラックの配合量が１００重量部をこえると、ゴム自身の発熱性が高くなり、耐久性が不充分となる傾向がある。 The compounding amount of carbon black is preferably 30 parts by weight or more, more preferably 40 parts by weight or more with respect to 100 parts by weight of the rubber component. If the blending amount of carbon black is less than 30 parts by weight, the reinforcing property of the rubber itself is insufficient, and the tensile strength tends to decrease. The amount of carbon black is preferably 100 parts by weight or less, more preferably 70 parts by weight or less. When the blending amount of the carbon black exceeds 100 parts by weight, the heat generation property of the rubber itself is increased and the durability tends to be insufficient.
本発明のコード被覆用ゴム組成物には、前記ゴム成分および超微粒子酸化亜鉛以外にも、従来ゴム工業で使用される配合剤、たとえば、カーボンブラックなどの補強用充填剤、軟化剤、ワックス、各種老化防止剤、ステアリン酸、硫黄などの加硫剤、各種加硫促進剤などを必要に応じて適宜配合することができる。 In addition to the rubber component and ultrafine zinc oxide, the rubber composition for cord coating of the present invention includes a compounding agent conventionally used in the rubber industry, for example, a reinforcing filler such as carbon black, a softener, a wax, Various anti-aging agents, vulcanizing agents such as stearic acid and sulfur, various vulcanization accelerators and the like can be appropriately blended as necessary.
本発明のコード被覆用ゴム組成物は、長期間良好な接着性を保ち、耐久性に優れるという理由から、コードのなかでも、ポリエステルコード、ナイロンコード、アラミドコード、ポリエチレンナフタレートを被覆して使用されるものである。なかでも、コードとしては、ポリエステルまたはナイロンが好ましく、ナイロンがより好ましい。 The rubber composition for cord coating of the present invention is used by coating polyester cord, nylon cord, aramid cord, polyethylene naphthalate among cords because it maintains good adhesion for a long time and is excellent in durability. It is what is done. Among these, as the cord, polyester or nylon is preferable, and nylon is more preferable.
本発明のタイヤは、本発明のコード被覆用ゴム組成物を用いて、通常の方法により製造することができる。すなわち、必要に応じて前記配合剤を配合した本発明のコード被覆用ゴム組成物を、未加硫の状態で、カレンダーロールなどを用いて、未加硫ゴムシートを作製し、コードを被覆することで未加硫カーカスおよび／または未加硫ベルトを作製し、タイヤの他の部材とともに、タイヤ成型機上にて通常の方法で成形することにより、未加硫タイヤを成形する。この未加硫タイヤを加硫機中で加熱加圧することにより本発明のタイヤを得る。 The tire of the present invention can be produced by an ordinary method using the rubber composition for cord coating of the present invention. That is, the cord coating rubber composition of the present invention blended with the above-described compounding agent as necessary is prepared in an unvulcanized state using a calender roll or the like to produce an unvulcanized rubber sheet and coat the cord. Thus, an unvulcanized carcass and / or an unvulcanized belt is prepared, and an unvulcanized tire is formed by forming it together with other members of the tire by a usual method on a tire molding machine. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain the tire of the present invention.
実施例にもとづいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
次に、実施例および比較例で使用した各種薬品について、まとめて説明する。
天然ゴム（ＮＲ）：ＲＳＳ♯３
スチレンブタジエンゴム（ＳＢＲ）：住友化学（株）製のＳＢＲ１５０２
カーボンブラック：三菱化学（株）製のダイアブラックＨ（Ｎ３３０）
アロマオイル：出光興産（株）製のダイアナプロセスＰＳ３２
酸化亜鉛：東邦亜鉛（株）製の銀嶺Ｒ（平均粒子径：２９０ｎｍ）
超微粒子酸化亜鉛：ハクスイテック（株）製のジンコックススーパーＦ−２（平均粒径：１３０ｎｍ）
ステアリン酸：日本油脂（株）製のステアリン酸「桐」
ワックス：日本精蝋（株）製のオゾエース０３５５
老化防止剤：住友化学（株）製のアンチゲン６Ｃ（Ｎ−（１，３−ジメチルブチル）−Ｎ−フェニル−ｐ−フェニレンジアミン）
硫黄：鶴見化学工業（株）製の粉末硫黄
加硫促進剤：大内新興化学工業（株）製のノクセラーＣＺ（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）
Next, various chemicals used in Examples and Comparative Examples will be described together.
Natural rubber (NR): RSS # 3
Styrene butadiene rubber (SBR): SBR1502 manufactured by Sumitomo Chemical Co., Ltd.
Carbon black: Dia Black H (N330) manufactured by Mitsubishi Chemical Corporation
Aroma oil: Diana Process PS32 manufactured by Idemitsu Kosan Co., Ltd.
Zinc oxide: Silver candy R (average particle size: 290 nm) manufactured by Toho Zinc Co., Ltd.
Ultrafine zinc oxide: Zincox Super F-2 (average particle size: 130 nm) manufactured by Hakusui Tech Co., Ltd.
Stearic acid: Stearic acid “paulownia” manufactured by NOF Corporation
Wax: Ozoace 0355 manufactured by Nippon Seiwa Co., Ltd.
Anti-aging agent: Antigen 6C (N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd .: Noxeller CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
実施例１〜３および比較例１〜４
表１に示す配合処方にしたがい、１．７Ｌのバンバリーミキサーを用いて、硫黄および加硫促進剤以外の薬品を１５０℃の条件下で５分間混練りし、混練り物を得た。次に、得られた混練り物に硫黄および加硫促進剤を添加し、２軸オープンロールを用いて、８０℃の条件下で５分間練り込み、未加硫ゴム組成物を得た。さらに、得られた未加硫ゴム組成物を１７０℃の条件下で１２分間プレス加硫することにより、実施例１〜３および比較例１〜４の加硫ゴム組成物を作成した。
Examples 1-3 and Comparative Examples 1-4
In accordance with the formulation shown in Table 1, using a 1.7 L Banbury mixer, chemicals other than sulfur and a vulcanization accelerator were kneaded for 5 minutes at 150 ° C. to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under a condition of 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition. Furthermore, the vulcanized rubber composition of Examples 1-3 and Comparative Examples 1-4 was created by press-curing the obtained unvulcanized rubber composition for 12 minutes on 170 degreeC conditions.
（屈曲亀裂成長試験）
ＪＩＳ Ｋ ６２６０「加硫ゴムおよび熱可塑性ゴムのデマッチャ屈曲亀裂成長試験方法」に準じて、室温２５℃の条件下で、加硫ゴム組成物に１ｍｍのクラックを発生させ、このクラックが１ｍｍ成長するまでの屈曲回数を測定した。なお、この測定は２回行い、その平均値を算出した。また、数値が大きいほど、耐屈曲亀裂成長性に優れ、７０％および１１０％は、もとの加硫ゴム組成物の長さに対する伸び率を示す。
(Bending crack growth test)
According to JIS K 6260 “Dematcher bending crack growth test method for vulcanized rubber and thermoplastic rubber”, a crack of 1 mm is generated in the vulcanized rubber composition at a room temperature of 25 ° C., and this crack grows by 1 mm. The number of bends up to was measured. In addition, this measurement was performed twice and the average value was computed. Moreover, the larger the value, the better the resistance to flex crack growth, and 70% and 110% indicate the elongation ratio with respect to the length of the original vulcanized rubber composition.
（接着試験）
ポリエステルコード（東レ（株）製、繊度：１５００ｄ／２）またはナイロンコード（旭化成（株）製、繊度：８４０ｄ／２）を前記未加硫ゴム組成物で被覆し、１７０℃の条件下で１２分間プレス加硫し、接着試験用試験片を作製した。
(Adhesion test)
Polyester cord (manufactured by Toray Industries, fineness: 1500d / 2) or nylon cord (manufactured by Asahi Kasei Co., Ltd., fineness: 840d / 2) is coated with the unvulcanized rubber composition, and the condition is 12 under the condition of 170 ° C. Press vulcanized for a minute to prepare a test piece for adhesion test.
前記試験片を用いて接着試験を実施し、ゴム組成物の剥離抗力（Ｎ／ｃｍ）およびゴム被覆率（％）をそれぞれ測定した。なお、ゴム被覆率とは、コードとゴム間を剥離したときの剥離面のゴムの覆われている割合（１００％：全面が覆われている）を示し、５段階（５：１００％、４：８５〜９９％、３：７０〜８４％、２：５０〜６９％、１：４９％以下）で評価した。 An adhesion test was performed using the test piece, and the peel resistance (N / cm) and the rubber coverage (%) of the rubber composition were measured. The rubber coverage is the ratio of the covered surface of the peeled rubber when the cord and the rubber are peeled (100%: the entire surface is covered), and has 5 levels (5: 100%, 4 : 85-99%, 3: 70-84%, 2: 50-69%, 1: 49% or less).
前記試験の評価結果を表１に示す。 The evaluation results of the test are shown in Table 1.
実施例１および２と、比較例１および２とを比較すると、通常の酸化亜鉛を配合した場合に比べて、超微粒子酸化亜鉛を配合すると、接着性に優れることがわかる。 When Examples 1 and 2 are compared with Comparative Examples 1 and 2, it can be seen that when ultrafine zinc oxide is blended, the adhesiveness is superior to that when blending ordinary zinc oxide.
実施例１と比較例３とを比較すると、超微粒子酸化亜鉛の配合量が１重量部未満では、接着性の充分な改善効果が得られないことがわかる。 When Example 1 and Comparative Example 3 are compared, it can be seen that if the blending amount of the ultrafine zinc oxide is less than 1 part by weight, a sufficient effect of improving adhesiveness cannot be obtained.
また、実施例３と比較例４とを比較すると、超微粒子酸化亜鉛の配合量が７重量部をこえると、耐カット性は向上しても、耐亀裂成長性が低下することがわかる。 Moreover, when Example 3 and Comparative Example 4 are compared, it can be seen that if the blending amount of the ultrafine zinc oxide exceeds 7 parts by weight, the crack growth resistance is lowered even if the cut resistance is improved.
Claims (2)
平均粒子径が３０〜２００ｎｍである超微粒子酸化亜鉛を３〜７重量部配合するポリエステルコード、ナイロンコード、アラミドコードまたはポリエチレンナフタレートコードを被覆するためのコード被覆用ゴム組成物。 For 100 parts by weight of a rubber component consisting of at least one selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber and ethylene propylene diene rubber ,
A rubber composition for coating a cord for coating a polyester cord, nylon cord, aramid cord or polyethylene naphthalate cord containing 3 to 7 parts by weight of ultrafine zinc oxide having an average particle size of 30 to 200 nm.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2006246815A JP5172120B2 (en) | 2006-09-12 | 2006-09-12 | Predetermined cord coating rubber composition and tire having carcass and / or belt using the same |
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| JP2006246815A JP5172120B2 (en) | 2006-09-12 | 2006-09-12 | Predetermined cord coating rubber composition and tire having carcass and / or belt using the same |
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| JP2008069199A JP2008069199A (en) | 2008-03-27 |
| JP5172120B2 true JP5172120B2 (en) | 2013-03-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011190409A (en) * | 2010-03-16 | 2011-09-29 | Sumitomo Rubber Ind Ltd | Rubber composition for breaker topping and pneumatic tire using the same |
| JP5848095B2 (en) * | 2011-11-04 | 2016-01-27 | 住友ゴム工業株式会社 | Rubber composition for breaker / ply strip layer and pneumatic tire |
| KR101527860B1 (en) * | 2013-08-16 | 2015-06-10 | 한국타이어 주식회사 | Rubber composition for carcass topping of tire and tire manufactured by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05222245A (en) * | 1992-02-10 | 1993-08-31 | Tokai Carbon Co Ltd | Rubber composition |
| JP3601559B2 (en) * | 1995-11-28 | 2004-12-15 | 日本ゼオン株式会社 | Diene rubber composition |
| JP3712019B2 (en) * | 1996-02-27 | 2005-11-02 | 日本ゼオン株式会社 | Rubber composition |
| JP2003146008A (en) * | 2001-11-09 | 2003-05-21 | Bridgestone Corp | Color solid tire |
| JP2003154821A (en) * | 2001-11-19 | 2003-05-27 | Bridgestone Corp | Run-flat tire |
| JP4289481B2 (en) * | 2003-04-23 | 2009-07-01 | 横浜ゴム株式会社 | Pneumatic radial tire |
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