JP2012153778A - Rubber composite, and tire using the same - Google Patents
Rubber composite, and tire using the same Download PDFInfo
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- JP2012153778A JP2012153778A JP2011013043A JP2011013043A JP2012153778A JP 2012153778 A JP2012153778 A JP 2012153778A JP 2011013043 A JP2011013043 A JP 2011013043A JP 2011013043 A JP2011013043 A JP 2011013043A JP 2012153778 A JP2012153778 A JP 2012153778A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 59
- 239000004760 aramid Substances 0.000 claims abstract description 45
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 45
- 239000010954 inorganic particle Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LVGKZTVMAHRVFR-UHFFFAOYSA-N 4-(phenoxazine-10-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C2OC2=CC=CC=C21 LVGKZTVMAHRVFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、耐久性に優れたゴム資材に関する。さらに詳しくは、無機粒子を含有する芳香族ポリアミド繊維を、ゴム複合体の厚み方向に対して特定本数垂直に配向させたゴム補強資材に関する。 The present invention relates to a rubber material excellent in durability. More specifically, the present invention relates to a rubber reinforcing material in which aromatic polyamide fibers containing inorganic particles are oriented perpendicularly to a specific number with respect to the thickness direction of the rubber composite.
従来、芳香族ジカルボン酸成分と芳香族ジアミン成分とからなる芳香族ポリアミド繊維（全芳香族ポリアミド繊維）、特にパラ系の芳香族ポリアミド繊維は、その強度、高弾性率、高耐熱性といった特性を活かして、ゴム補強に好適に用いられている。 Conventionally, aromatic polyamide fibers (totally aromatic polyamide fibers) composed of an aromatic dicarboxylic acid component and an aromatic diamine component, particularly para-type aromatic polyamide fibers, have characteristics such as strength, high elastic modulus, and high heat resistance. Utilizing it, it is suitably used for rubber reinforcement.
ゴム補強として代表的な芳香族ポリアミド繊維としては、ポリパラフェニレンテレフタルアミド（ＰＰＴＡ）繊維やコポリパラフェニレン・３，４’−オキシジフェニレンテレフタルアミド繊維がある。これらの繊維は多くの利点を有し、高機能タイヤの補強等にも活用されている。しかしながら、雪面等の摩擦係数の低い路面等ではゴム資材での滑りが生じ、より高性能な雪面用タイヤを作ることが困難であった。 Typical aromatic polyamide fibers for rubber reinforcement include polyparaphenylene terephthalamide (PPTA) fiber and copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber. These fibers have many advantages and are used for reinforcing high-performance tires. However, on a road surface with a low coefficient of friction such as a snow surface, slipping with a rubber material occurs, making it difficult to produce a snow tire with higher performance.
このような課題を解決するため、例えば特許文献１、２にはタイヤ用ゴム組成物に無機フィラーを添加する方法が提案されている。
しかしながら、上記方法では、高い摩擦係数のゴム複合体が得られるものの、耐摩耗性が悪く、無機微粒子が飛散するなどの問題が生じる。
In order to solve such a problem, for example, Patent Documents 1 and 2 propose a method of adding an inorganic filler to a tire rubber composition.
However, although the rubber composite having a high friction coefficient can be obtained by the above method, there are problems such as poor wear resistance and scattering of inorganic fine particles.
本発明は、かかる従来技術を背景になされたもので、その目的は、摩擦係数が高く、且つ耐摩耗性に優れたゴム複合体を提供することにある。また、上記特性を備え雪面等で性能を発揮するタイヤを提供することにある。 The present invention has been made against the background of such prior art, and an object thereof is to provide a rubber composite having a high coefficient of friction and excellent wear resistance. Another object of the present invention is to provide a tire having the above characteristics and exhibiting performance on a snow surface or the like.
本発明者は、上記課題を解決するため鋭意検討を行った。その結果、無機粒子を含有する芳香族ポリアミド繊維をゴム複合体の厚さ方向に対して特定本数垂直方向に配向させたゴム複合体を用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventor has intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by using a rubber composite in which aromatic polyamide fibers containing inorganic particles are oriented in a direction perpendicular to the thickness direction of the rubber composite. It came to be completed.
即ち本発明によれば、
繊維とゴムからなるシート状ゴム複合体の多層積層体であって、下記要件を満足することを特徴とするゴム複合体、
ａ）平均粒径０．５〜１０μｍの無機粒子を５〜５０重量％含有する芳香族ポリアミド短繊維を含有すること。
ｂ）厚さが２〜２００ｍｍであり、厚さ方向に対して８５°〜９５°の角度で配向している芳香族ポリアミド短繊維の本数が５０〜５００本／ｍｍ３であること。
また、別の発明の態様として、該ゴム複合体を含むタイヤ、
が提供される。
That is, according to the present invention,
A multilayer laminate of a sheet-like rubber composite made of fiber and rubber, which satisfies the following requirements:
a) It contains an aromatic polyamide short fiber containing 5 to 50% by weight of inorganic particles having an average particle size of 0.5 to 10 μm.
b) The thickness is 2 to 200 mm, and the number of aromatic polyamide short fibers oriented at an angle of 85 ° to 95 ° with respect to the thickness direction is 50 to 500 / mm 3 .
As another aspect of the invention, a tire including the rubber composite,
Is provided.
本発明のゴム複合体は、摩擦係数が高く且つ耐摩耗性に優れる。このため、凍結路面等での操縦安定性に優れており、雪面タイヤ用途に非常に有用である。 The rubber composite of the present invention has a high friction coefficient and excellent wear resistance. For this reason, it is excellent in handling stability on a frozen road surface or the like, and is very useful for snow surface tire applications.
以下、本発明の実施の形態について詳細に説明する。
本発明のゴム複合体はゴム成分及び芳香族ポリアミド繊維（アラミド繊維と呼ぶ場合がある）からなる。本発明に用いられるゴムとしては、天然ゴム、ポリイソプレンゴム、各種スチレン−ブタジエン共重合ゴム、各種ポリブタジエンゴム及び各種ハロゲン化ゴム等が挙げられる。なかでも、天然ゴム及びポリブタジエンゴムは発熱性能が良好であることから好ましい。
Hereinafter, embodiments of the present invention will be described in detail.
The rubber composite of the present invention comprises a rubber component and an aromatic polyamide fiber (sometimes called an aramid fiber). Examples of the rubber used in the present invention include natural rubber, polyisoprene rubber, various styrene-butadiene copolymer rubbers, various polybutadiene rubbers, and various halogenated rubbers. Of these, natural rubber and polybutadiene rubber are preferable because they have good heat generation performance.
本発明において用いられるアラミド繊維は、アラミドポリマーと無機粒子を溶媒中で混合した後に成型された繊維に、必要に応じて処理剤を付与し均一な長さでカットすることにより製造することができる。 The aramid fiber used in the present invention can be produced by adding a treatment agent to the molded fiber after mixing the aramid polymer and inorganic particles in a solvent and cutting it to a uniform length as necessary. .
なお、アラミドポリマーへ無機粒子をブレンドする際は、該無機粒子の凝集を抑制する必要がある。このため、アラミドポリマードープを調製するに際し、その方法は特に限定されるものではないが、無機粒子分散液を、アラミドポリマー溶液に一定の圧力で注入し、ダイナミックミキシングおよび／またはスタティックミキシングする方法が好ましい。 In addition, when blending an inorganic particle with an aramid polymer, it is necessary to suppress aggregation of the inorganic particle. For this reason, when preparing an aramid polymer dope, the method is not particularly limited, but there is a method in which an inorganic particle dispersion is injected into an aramid polymer solution at a constant pressure to perform dynamic mixing and / or static mixing. preferable.
本発明に用いられる無機粒子は、酸化鉄、酸化チタン、タングステン、酸化マグネシウム、酸化亜鉛、酸化銅などを好ましく例示することができる。無機粒子の平均粒径は１０μｍ以下が好ましく、さらに好ましくは８μｍ以下である。平均粒径が１０μｍを超えると無機粒子が芳香族ポリアミド繊維から脱落するため本発明の効果が得られず好ましくない。 Preferred examples of the inorganic particles used in the present invention include iron oxide, titanium oxide, tungsten, magnesium oxide, zinc oxide, and copper oxide. The average particle size of the inorganic particles is preferably 10 μm or less, more preferably 8 μm or less. If the average particle diameter exceeds 10 μm, the inorganic particles fall off from the aromatic polyamide fiber, and the effect of the present invention cannot be obtained, which is not preferable.
芳香族ポリアミド繊維に含まれる無機粒子の含有量は５〜５０重量％が好ましく、さらに好ましくは１０〜４０重量％である。無機粒子の含有量が５重量％未満では無機粒子による芳香族ポリアミド繊維の補強効果が無く耐磨耗性が低下するため好ましくない。また、無機粒子の含有量が５０重量％を超えると芳香族ポリアミド繊維中に無機粒子が均一に分散せず、無機粒子の脱落が生じるため好ましくない。 The content of the inorganic particles contained in the aromatic polyamide fiber is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the content of the inorganic particles is less than 5% by weight, the aromatic polyamide fiber is not reinforced by the inorganic particles and the wear resistance is lowered, which is not preferable. Further, if the content of the inorganic particles exceeds 50% by weight, the inorganic particles are not uniformly dispersed in the aromatic polyamide fiber, and the inorganic particles fall off, which is not preferable.
上記芳香族ポリアミド繊維の具体例としては、芳香族ジカルボン酸成分と芳香族ジアミン成分、もしくは芳香族アミノカルボン酸成分から構成されるアラミドポリマー、またはこれらの共重合アラミドポリマーからなる繊維であり、例えばポリパラフェニレンテレフタルアミド繊維、コポリパラフェニレン・３，４’−オキシジフェニレンテレフタルアミド繊維、ポリメタフェニレンテレフタルアミド繊維などが例示できる。なかでも、コポリパラフェニレン・３，４’−オキシジフェニレンテレフタルアミド繊維が高い強度を有すると同時に耐久性に優れているので特に好ましい。 Specific examples of the aromatic polyamide fiber include an aramid polymer composed of an aromatic dicarboxylic acid component and an aromatic diamine component, or an aromatic aminocarboxylic acid component, or a fiber composed of a copolymer aramid polymer, for example, Examples thereof include polyparaphenylene terephthalamide fiber, copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber, and polymetaphenylene terephthalamide fiber. Among them, the copolyparaphenylene • 3,4′-oxydiphenylene terephthalamide fiber is particularly preferable because it has high strength and excellent durability.
また、得られた芳香族ポリアミド繊維をゴムへ添加する方法は特に限定されるものではないが、オープンロール、加圧ニーダー、バンバリーミキサーで混練することが好ましい。 The method of adding the obtained aromatic polyamide fiber to the rubber is not particularly limited, but it is preferably kneaded with an open roll, a pressure kneader, or a Banbury mixer.
混練後、芳香族ポリアミド繊維およびゴム混練物をオープンロールでシート状に成型することが好ましい。ここでオープンロールの間隙を調整してシート状ゴム複合体（ゴムシートと呼ぶ場合がある）の厚みを２ｍｍ以下とすることが好ましい。２ｍｍ以下とする時、芳香族ポリアミド短繊維がシート送り出し方向に均一に配向する（厚さ方向に対して垂直方向に配向する）ため好ましい。芳香族ポリアミド短繊維がロール間隙を通過する際にせん断力により芳香族ポリアミド短繊維がシート厚さ方向に対して垂直方向に配向しやすい。一方ゴムシートの厚さが２ｍｍを超えると芳香族ポリアミド短繊維の配向が不均一となるため好ましくない。
ここで厚さ方向に対して垂直方向とは、厚さ方向に対して８５°〜９５°の角度で配向していることを意味する。
After kneading, the aromatic polyamide fiber and the rubber kneaded material are preferably formed into a sheet shape with an open roll. Here, it is preferable to adjust the gap between the open rolls so that the thickness of the sheet-like rubber composite (sometimes referred to as a rubber sheet) is 2 mm or less. When the length is 2 mm or less, the aromatic polyamide short fibers are preferably uniformly oriented in the sheet feeding direction (orientated in the direction perpendicular to the thickness direction). When the aromatic polyamide short fibers pass through the roll gap, the aromatic polyamide short fibers are easily oriented in the direction perpendicular to the sheet thickness direction due to the shearing force. On the other hand, if the thickness of the rubber sheet exceeds 2 mm, the orientation of the aromatic polyamide short fibers becomes non-uniform, which is not preferable.
Here, the direction perpendicular to the thickness direction means that the film is oriented at an angle of 85 ° to 95 ° with respect to the thickness direction.
このようにして得られたゴムシートを繊維が同一方向に配向するように積層して多層積層体とし、積層ゴムシートを芳香族ポリアミド繊維配向方向と垂直に均等な厚みとなるように切断し、求める形状に並べた後、蒸気加硫又はプレス加硫により成型することにより芳香族ポリアミド繊維が厚さ方向に対して垂直方向に配向したゴム複合体が得られる。 The rubber sheet thus obtained is laminated so that the fibers are oriented in the same direction to form a multilayer laminate, and the laminated rubber sheet is cut so as to have a uniform thickness perpendicular to the orientation direction of the aromatic polyamide fiber, After arranging in a desired shape, a rubber composite in which aromatic polyamide fibers are oriented in a direction perpendicular to the thickness direction is obtained by molding by steam vulcanization or press vulcanization.
また、タイヤに用いる場合は、上記シート状ゴム複合体をタイヤ製造工程において、トレッド部に積層した後、加硫成型することで芳香族ポリアミド繊維が厚さ方向に対して垂直方向に配向したタイヤが得られる。 Further, when used for a tire, in the tire manufacturing process, the sheet-like rubber composite is laminated on a tread portion, and then vulcanized to form an aromatic polyamide fiber oriented in a direction perpendicular to the thickness direction. Is obtained.
ゴム複合体の厚さ方向に対して垂直方向に配向している芳香族ポリアミド繊維の本数は１ｍｍ３あたり５０〜５００本が好ましく、さらに好ましくは１００〜４００本である。
ゴム複合体の厚さ方向に対して垂直方向に配向している芳香族ポリアミド繊維の本数が１ｍｍ３あたり５０本未満では芳香族ポリアミド繊維の補強効果が無く耐摩耗性が低下するため好ましくない。また、ゴム複合体厚さ方向に対して垂直方向に配向している芳香族ポリアミド繊維の本数が１ｍｍ３あたり５００本を超えると外部と接触するゴムの表面積が減り摩擦係数が低下するため好ましくない。
The number of aromatic polyamide fibers oriented in the direction perpendicular to the thickness direction of the rubber composite is preferably 50 to 500, more preferably 100 to 400, per mm 3 .
If the number of aromatic polyamide fibers oriented in a direction perpendicular to the thickness direction of the rubber composite is less than 50 per 1 mm 3 , the aromatic polyamide fibers have no reinforcing effect and wear resistance is lowered, which is not preferable. In addition, if the number of aromatic polyamide fibers oriented in the direction perpendicular to the thickness direction of the rubber composite exceeds 500 per 1 mm 3 , the surface area of the rubber in contact with the outside is reduced, and the friction coefficient is lowered, which is not preferable. .
以下、実施例をあげて本発明をさらに具体的に説明するが、本発明はこれらによって限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
＜測定・評価方法＞
実施例および比較例における各特性値は、以下の方法により測定・評価を行った。
（１）ゴム複合体厚さ方向に対して垂直方向に配向している芳香族ポリアミド繊維の本数
試験タイヤのトレッド部から５ｃｍ×２ｃｍのサンプルを切り出し、神鋼株式会社製スライサーで厚み０．５ｍｍのシートに削り、目視で厚さ方向に対して垂直方向に配向している繊維本数を数え、サンプルの体積当たりの数値を算出した。
（２）動摩擦係数
試験タイヤを神戸機械社製の転がり抵抗試験機で、荷重３６５ｋｇｆ、内圧２９０ｋＰａ、速度８０ｋｍ／時で走行させ、転がり抵抗を測定し、実施例１を１００とする指数で評価した。
（３）耐摩耗性
試験タイヤを、荷重１７８ｋｇｆ、内圧２９０ｋＰａの条件で１０分間同じ速度でドラム上を走行させるとともに、速度を１０ｋｍ／時で加速させ、速度２７０ｋｍ／時まで走行させ、完走を合格、途中バーストしたものを不合格とした。
<Measurement and evaluation method>
Each characteristic value in Examples and Comparative Examples was measured and evaluated by the following method.
(1) Number of aromatic polyamide fibers oriented in a direction perpendicular to the thickness direction of the rubber composite A 5 cm × 2 cm sample was cut out from the tread portion of the test tire, and 0.5 mm thick with a slicer manufactured by Shinko Co., Ltd. The number of fibers oriented in the direction perpendicular to the thickness direction was counted by cutting into a sheet, and the numerical value per volume of the sample was calculated.
(2) Coefficient of dynamic friction The test tire was run with a rolling resistance tester manufactured by Kobe Machinery Co., Ltd., with a load of 365 kgf, an internal pressure of 290 kPa, and a speed of 80 km / hour, and the rolling resistance was measured. .
(3) Abrasion resistance The test tire was run on the drum at the same speed for 10 minutes under the conditions of a load of 178 kgf and an internal pressure of 290 kPa, and the speed was accelerated at 10 km / hour and was run to a speed of 270 km / hour. Anything that burst in the middle was rejected.
［実施例１］
（芳香族ポリアミド繊維の作成）
平均粒径８μｍの酸化鉄にＮ−メチルピロリドンを添加混合して酸化鉄が１０重量％のＮ−メチルピロリドン溶液を作成した。この酸化鉄分散液をコポリパラフェニレン−３，４’オキシジフェニレンテレフタルアミドの６重量％のＮ−メチルピロリドン溶液に対して、酸化鉄が繊維全重量に対して２０重量％になるように添加して紡糸原液を作成し、孔径０．３ｍｍでホール数６６７のノズルから吐出し半乾半湿式紡糸法により紡糸し、水洗乾燥後１０倍に延伸し５５０℃で熱セットして製糸し芳香族ポリアミド長繊維を得た。カットして単糸繊度１．６７ｄｔｅｘ、長さ３ｍｍの短繊維を得た。
[Example 1]
(Creation of aromatic polyamide fiber)
N-methylpyrrolidone was added to and mixed with iron oxide having an average particle diameter of 8 μm to prepare an N-methylpyrrolidone solution containing 10% by weight of iron oxide. This iron oxide dispersion was added to a 6 wt% N-methylpyrrolidone solution of copolyparaphenylene-3,4′oxydiphenylene terephthalamide so that the iron oxide was 20 wt% based on the total weight of the fiber. A spinning undiluted solution is prepared, discharged from a nozzle having a hole diameter of 0.3 mm and having a hole number of 667, spun by a semi-dry semi-wet spinning method, washed with water and dried, stretched 10 times, and heat-set at 550 ° C. to produce a yarn. A polyamide long fiber was obtained. Cut to obtain a short fiber having a single yarn fineness of 1.67 dtex and a length of 3 mm.
（ゴム複合体の作成）
クロロプレンゴム５００ｇにゴム添加剤２５０ｇを加え加圧ニーダーで１０分混練した後、上記の芳香族ポリアミド短繊維２００ｇを加えさらに加圧ニーダーで１５分混練した。
この芳香族ポリアミド繊維混練ゴムに２０ｇの酸化亜鉛と１０ｇの酸化マグネシウムを加硫剤として添加しオープンロールで１０分混練した後、厚み１．５ｍｍのゴムシートを得た。得られたゴムシート中の繊維はローラー進行方向に配向していた。本ゴムシートを２０枚積層した積層体を繊維垂直方向に４０ｍｍ間隔でカットしたゴム複合体を隙間無く並べることによりシート状の複合体を得た。
(Create rubber composite)
After adding 250 g of a rubber additive to 500 g of chloroprene rubber and kneading with a pressure kneader for 10 minutes, 200 g of the above aromatic polyamide short fibers were added and further kneaded with a pressure kneader for 15 minutes.
After adding 20 g of zinc oxide and 10 g of magnesium oxide as a vulcanizing agent to this aromatic polyamide fiber kneaded rubber and kneading with an open roll for 10 minutes, a rubber sheet having a thickness of 1.5 mm was obtained. The fibers in the obtained rubber sheet were oriented in the roller traveling direction. A sheet-like composite was obtained by arranging a rubber composite obtained by laminating 20 sheets of the present rubber sheet at intervals of 40 mm in the fiber vertical direction without gaps.
（タイヤの作成）
タイヤは、剛性コアの外面上にカーカスコード延在させ、該カーカスの両端部をビードコアの周りで折り返し、次いで該カーカスのクラウン部の外周上に、内外二層のスチールコード層よりなるベルトを配設することでベルト補強層を配設した後、サイドゴム、トレッドゴムを配置して生タイヤを成形した。
この生タイヤのトレッドゴムに前記のゴム複合体を用いた。生タイヤを所定のモールド中で加硫することにより、タイヤを得た。
得られたタイヤ最外層のトレッド部ゴム複合体中のゴム複合体厚さ方向に対して垂直に配向している芳香族ポリアミド繊維の本数は１ｍｍ３あたり２２０本であった。該タイヤの評価結果を表１にまとめた。
(Tire creation)
The tire extends the carcass cord on the outer surface of the rigid core, folds both ends of the carcass around the bead core, and then arranges a belt composed of two inner and outer steel cord layers on the outer periphery of the crown portion of the carcass. After the belt reinforcing layer was disposed, a side rubber and a tread rubber were disposed to form a green tire.
The rubber composite was used as the tread rubber of this green tire. The raw tire was vulcanized in a predetermined mold to obtain a tire.
The number of aromatic polyamide fibers oriented perpendicular to the thickness direction of the rubber composite in the tread portion rubber composite of the outermost tire layer obtained was 220 per 1 mm 3 . The evaluation results of the tire are summarized in Table 1.
［比較例１］
酸化鉄の平均粒径が１５μｍであること以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 1]
A tire was obtained in the same manner as in Example 1 except that the average particle size of iron oxide was 15 μm. The evaluation results are summarized in Table 1.
［比較例２］
酸化鉄の添加量が３重量％であること以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 2]
A tire was obtained in the same manner as in Example 1 except that the amount of iron oxide added was 3% by weight. The evaluation results are summarized in Table 1.
［比較例３］
酸化鉄の添加量が５５重量％であること以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 3]
A tire was obtained in the same manner as in Example 1 except that the amount of iron oxide added was 55% by weight. The evaluation results are summarized in Table 1.
［比較例４］
芳香族ポリアミド繊維の添加量が１００ｇであること以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 4]
A tire was obtained in the same manner as in Example 1 except that the amount of the aromatic polyamide fiber added was 100 g. The evaluation results are summarized in Table 1.
［比較例５］
芳香族ポリアミド繊維の添加量が７００ｇであること以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 5]
A tire was obtained in the same manner as in Example 1 except that the amount of the aromatic polyamide fiber added was 700 g. The evaluation results are summarized in Table 1.
［比較例６］
ゴムシートの厚みが３ｍｍであること以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 6]
A tire was obtained in the same manner as in Example 1 except that the rubber sheet had a thickness of 3 mm. The evaluation results are summarized in Table 1.
［比較例７］
芳香族ポリアミド繊維を加えなかったこと以外は実施例１と同様にしてタイヤを得た。評価結果は表１にまとめた。
[Comparative Example 7]
A tire was obtained in the same manner as in Example 1 except that the aromatic polyamide fiber was not added. The evaluation results are summarized in Table 1.
本発明のゴム複合体は、摩擦係数が高く、且つ耐摩耗性に優れており、かかる性能を必要とするタイヤ、ベルト等のゴム資材に広く用いることができる。特に、上記ゴム複合体を用いた本発明のタイヤは、上記特性を備え雪面等で性能を遺憾なく発揮する。 The rubber composite of the present invention has a high coefficient of friction and excellent wear resistance, and can be widely used for rubber materials such as tires and belts that require such performance. In particular, the tire of the present invention using the rubber composite has the above characteristics and exhibits performance on the snow surface or the like.
Claims (2)
ａ）平均粒径０．５〜１０μｍの無機粒子を５〜５０重量％含有する芳香族ポリアミド短繊維を含有すること。
ｂ）厚さが２〜２００ｍｍであり、厚さ方向に対して８５°〜９５°の角度で配向している芳香族ポリアミド短繊維の本数が５０〜５００本／ｍｍ３であること。 A rubber composite comprising a multilayered laminate of sheet-like rubber composites comprising fibers and rubbers, wherein the following requirements are satisfied.
a) It contains an aromatic polyamide short fiber containing 5 to 50% by weight of inorganic particles having an average particle size of 0.5 to 10 μm.
b) The thickness is 2 to 200 mm, and the number of aromatic polyamide short fibers oriented at an angle of 85 ° to 95 ° with respect to the thickness direction is 50 to 500 / mm 3 .
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101791890B1 (en) * | 2016-03-18 | 2017-11-01 | 한국타이어 주식회사 | Rubber composition with heating textile and tire using the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101791890B1 (en) * | 2016-03-18 | 2017-11-01 | 한국타이어 주식회사 | Rubber composition with heating textile and tire using the same |
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