JP2008260889A - Foamed rubber, tire and shoes comprising the same - Google Patents
Foamed rubber, tire and shoes comprising the same Download PDFInfo
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本発明は、発泡ゴム、並びに該発泡ゴムを具えたタイヤ及び靴に関し、特に氷雪路面上でのグリップ性に優れ、滑り難い発泡ゴムに関するものである。 The present invention relates to foamed rubber, and tires and shoes provided with the foamed rubber, and more particularly to foamed rubber that is excellent in grip on an icy and snowy road surface and hardly slips.
通常の路面上に加え、氷上や雪上でも走行するために使用されるスタッドレスタイヤの氷上性能を向上させるために、これまで、種々のスタッドレスタイヤ用のトレッドゴムが開発されてきた。例えば、トレッドゴムとして発泡ゴムを用い、該発泡ゴム中の気泡がポリエチレン皮膜で囲まれているタイヤが知られている。該タイヤにおいては、気泡が効率的な排水を行うためのミクロな排水路として機能すると共に、ポリエチレン皮膜が排水路の形状保持性等を向上させる結果として、タイヤの氷上性能が向上している。しかしながら、該タイヤにおいては、トレッドの水膜除去能は向上するものの、エッヂ効果及びスパイク効果が十分に向上しておらず、氷上性能に改良の余地があった。 Various tread rubbers for studless tires have been developed so far in order to improve the on-ice performance of studless tires used for running on ice and snow in addition to normal road surfaces. For example, a tire is known in which foamed rubber is used as the tread rubber, and bubbles in the foamed rubber are surrounded by a polyethylene film. In the tire, the air bubbles function as a micro drainage channel for efficient drainage, and as a result of the polyethylene film improving the shape retaining property of the drainage channel, the on-ice performance of the tire is improved. However, in the tire, although the water film removing ability of the tread is improved, the edge effect and the spike effect are not sufficiently improved, and there is room for improvement in performance on ice.
これに対して、特開２００３−２０１３７１号公報（特許文献１）には、ゴムマトリックスとモース硬度が２以上の微粒子を含有する微粒子含有有機繊維とかなるゴム組成物が開示されており、該ゴム組成物をトレッドに用いることで、トレッドの水膜除去能を向上させつつ、エッヂ効果及びスパイク効果を向上させられることが開示されている。 On the other hand, Japanese Patent Application Laid-Open No. 2003-201371 (Patent Document 1) discloses a rubber composition comprising a rubber matrix and fine particle-containing organic fibers containing fine particles having a Mohs hardness of 2 or more. It is disclosed that the edge effect and the spike effect can be improved while improving the water film removing ability of the tread by using the composition in the tread.
ここで、タイヤの氷上性能の更なる向上には、微粒子含有有機繊維に含有させる微粒子を増量することが効果的である。しかしながら、微粒子を増量すると、トレッド面の押出肌が悪化したり、加硫後にスピュー詰まり等が発生したり、タイヤの耐摩耗性が悪化するなどの問題がある。 Here, in order to further improve the performance on ice of the tire, it is effective to increase the amount of fine particles contained in the fine particle-containing organic fiber. However, when the amount of fine particles is increased, there are problems such that the extruded skin of the tread surface deteriorates, spew clogging occurs after vulcanization, and the tire wear resistance deteriorates.
この問題に対して、特開２００６−２７４１３６号公報（特許文献２）には、微粒子を含まない有機繊維と微粒子を含有する有機粒子とを含む発泡ゴム層をトレッドに具えたタイヤが開示されている。そして、該発泡ゴム層においては、微粒子含有有機粒子を使用しつつ有機繊維量を低減することで、押出外観が改良されると共に、加硫後のスピュー詰まり等が防止されており、更に、該発泡ゴム層を具えたタイヤにおいては、トレッド面の押出肌が良好である上、微粒子の脱離による耐摩耗性の低下が抑制される等の効果が奏されることが開示されている。 In order to solve this problem, Japanese Patent Application Laid-Open No. 2006-274136 (Patent Document 2) discloses a tire having a tread having a foam rubber layer including organic fibers not containing fine particles and organic particles containing fine particles. Yes. And, in the foamed rubber layer, by reducing the amount of organic fibers while using fine particle-containing organic particles, the extrusion appearance is improved and spew clogging after vulcanization is prevented, It is disclosed that a tire provided with a foamed rubber layer has good effects such as excellent extruding skin on the tread surface and suppressing a decrease in wear resistance due to detachment of fine particles.
上記のように、従来の発泡ゴムをトレッドに具えるタイヤは、トレッドの水膜除去能、エッヂ効果及びスパイク効果を向上させて、氷上性能を向上させるものであり、精力的な研究開発により、一応の成果を上げている。しかしながら、スタッドレスタイヤの氷上性能を抜本的に向上させるには、従来知られている効果のレベルを上げるだけでは限界がある。 As mentioned above, the tire with the conventional foam rubber in the tread improves the performance on ice by improving the water film removal ability, edge effect and spike effect of the tread, and through vigorous research and development, Has achieved some results. However, in order to drastically improve the performance on ice of a studless tire, there is a limit only by raising the level of the effect known conventionally.
そこで、本発明は、従来と全く異質な作用効果を有し、氷雪路面上でのグリップ性に優れ、滑り難く、特にタイヤのトレッドや靴の靴底に好適な発泡ゴムを提供することを目的とする。 Accordingly, the present invention has an object to provide a foamed rubber which has a completely different effect from conventional ones, is excellent in grip on an icy and snowy road surface, is hard to slip, and is particularly suitable for a tire tread or a shoe sole. And
本発明者は、上記目的を達成するために鋭意検討した結果、独立気泡を含み、該独立気泡が表面層で囲まれている発泡ゴムにおいて、吸盤の減圧吸着原理を応用して、独立気泡を囲む表面層に親水性を付与することで、発泡ゴムの平滑面への吸着能が大幅に向上し、該発泡ゴムをタイヤのトレッドに使用することで、タイヤの氷雪路面上でのグリップ性が大幅に向上し、また、該発泡ゴムを靴の靴底に使用することで、靴が氷雪路面上でも滑り難くなることを見出し、本発明を完成させるに至った。 As a result of intensive investigations to achieve the above object, the present inventor applied closed-cells to the foamed rubber containing closed cells, and the closed cells were surrounded by a surface layer. By imparting hydrophilicity to the surrounding surface layer, the ability of foamed rubber to adsorb to the smooth surface is greatly improved, and by using the foamed rubber for a tire tread, the grip performance of the tire on snowy and snowy road surfaces can be improved. The present invention has been greatly improved, and it has been found that the use of the foamed rubber for the sole of the shoe makes it difficult for the shoe to slip even on an icy and snowy road surface, thereby completing the present invention.
即ち、本発明の発泡ゴムは、独立気泡を含み、該独立気泡が表面層で囲まれており、該独立気泡を囲む表面層が親水性を有することを特徴とする。 That is, the foamed rubber of the present invention includes closed cells, the closed cells are surrounded by a surface layer, and the surface layer surrounding the closed cells is hydrophilic.
本発明の発泡ゴムの好適例においては、前記独立気泡を囲む表面層が極性基を有する。ここで、該極性基は、水素結合能を有することが好ましく、また、該極性基としては、イオン性官能基が好ましい。 In a preferred example of the foam rubber of the present invention, the surface layer surrounding the closed cells has a polar group. Here, the polar group preferably has hydrogen bonding ability, and the polar group is preferably an ionic functional group.
本発明の発泡ゴムの他の好適例においては、前記独立気泡を囲む表面層がイオン性ポリマーからなる。 In another preferred embodiment of the foam rubber of the present invention, the surface layer surrounding the closed cells is made of an ionic polymer.
本発明の発泡ゴムの他の好適例においては、前記表面層を構成する材料の融点が200℃以下である。この場合、発泡ゴム用ゴム組成物の加硫工程で、表面層用材料が独立気泡とゴムマトリックスとの界面に析出して、独立気泡を親水性の表面層で容易に囲むことができる。 In another preferred embodiment of the foam rubber of the present invention, the material constituting the surface layer has a melting point of 200 ° C. or lower. In this case, in the vulcanization process of the rubber composition for foamed rubber, the surface layer material is deposited at the interface between the closed cells and the rubber matrix, and the closed cells can be easily surrounded by the hydrophilic surface layer.
本発明の発泡ゴムの他の好適例においては、前記表面層の表面エネルギーが30mJ/m2以上である。この場合、独立気泡がポリエチレンで囲まれている発泡ゴムよりも、氷雪路面に対する吸着力を確実に向上させることができる。 In another preferred embodiment of the foam rubber of the present invention, the surface energy of the surface layer is 30 mJ / m 2 or more. In this case, the adsorbing force on the snowy and snowy road surface can be improved more reliably than the foamed rubber in which the closed cells are surrounded by polyethylene.
また、本発明のタイヤは、トレッドゴムとして上記の発泡ゴムを具えることを特徴とし、本発明の靴は、靴底として上記の発泡ゴムを具えることを特徴とする。 The tire of the present invention is characterized by comprising the above-mentioned foamed rubber as a tread rubber, and the shoe of the present invention is characterized by comprising the above-mentioned foamed rubber as a shoe sole.
本発明によれば、独立気泡を含み、該独立気泡が表面層で囲まれている発泡ゴムにおいて、独立気泡を囲む表面層に親水性を付与することで、発泡ゴムの平滑面への吸着能を大幅に向上させることができる。また、該発泡ゴムをタイヤのトレッドに使用することで、タイヤの氷雪路面上でのグリップ性を大幅に向上させることができ、該発泡ゴムを靴の靴底に使用することで、靴が氷雪路面上でも大幅に滑り難くなる。 According to the present invention, in the foamed rubber containing closed cells, and the closed cells are surrounded by the surface layer, the hydrophilic property is imparted to the surface layer surrounding the closed cells, thereby allowing the foam rubber to adsorb to the smooth surface. Can be greatly improved. Further, the use of the foamed rubber for a tire tread can greatly improve the grip performance of the tire on a snowy road surface, and the use of the foamed rubber for the shoe sole of the shoe enables the shoe to be snowy. Even on the road surface, it becomes much harder to slip.
以下に、本発明を詳細に説明する。図１は、本発明の発泡ゴムの部分断面図である。本発明の発泡ゴム１は、独立気泡２を含み、該独立気泡２が表面層３で囲まれており、該独立気泡を囲む表面層３が親水性を有することを特徴とする。本発明においては、吸盤の理論を応用して、発泡ゴム内に液体を充満させた状態で一部の液体を外部からの入力により外部に排出させ、発泡ゴム内を負圧状態にすることで、発泡ゴムを氷雪路面等の平滑面に吸着させる。
The present invention is described in detail below. FIG. 1 is a partial cross-sectional view of the foam rubber of the present invention. The foamed rubber 1 according to the present invention is characterized in that it includes closed
物体を平滑面に固定または滑り難くする方法として、吸盤の技術が存在する。該吸盤においては、吸盤内の気圧が外部気圧よりも低くなることで、物体が平滑面に固定される。一般に、閉空間に閉じ込められた気体や液体の体積変化によって、以下の式(I)：
ｄｐ＝−Ｋ・（ｄｖ／ｖ） ・・・ (I)
に従って、圧力変化が生じる。ここで、ｄｖは体積ｖに対する微小体積変化を表わし、ｄｐはこの体積変化によって生じる圧力変化を表わし、比例定数Ｋは体積弾性率を表わす。そして、本発明においては、外圧により微小体積ｄｖの液体を発泡ゴムの外部に排出させることで、発泡ゴムに内部負圧ｄｐを発生させて、発泡ゴムを氷雪路面等の平滑面に吸着させる。
A suction cup technique exists as a method of fixing an object to a smooth surface or making it difficult to slip. In the suction cup, the object is fixed to the smooth surface by the pressure inside the suction cup being lower than the external pressure. In general, depending on the volume change of gas or liquid confined in a closed space, the following formula (I):
dp = −K · (dv / v) (I)
As a result, a pressure change occurs. Here, dv represents a minute volume change with respect to the volume v, dp represents a pressure change caused by the volume change, and a proportionality constant K represents a bulk modulus. In the present invention, a liquid having a minute volume dv is discharged to the outside of the foamed rubber by an external pressure, thereby generating an internal negative pressure dp in the foamed rubber, and the foamed rubber is adsorbed on a smooth surface such as an icy and snowy road surface.
上記体積弾性率Ｋに関して、水（1気圧、20℃）の体積弾性率Ｋは2.06×109（Pa）であり、空気（1気圧）の体積弾性率Ｋは1.4×105（Pa）である。従って、水は、空気に比べて15000倍の体積弾性率Ｋを有し、空気に比べて微小の体積変化で大きな負圧力を生じて、大きな吸盤効果を示す。ここで、吸盤の開口部に発生する吸着力Ｆは、開口部の面積をＳとすると、ｄｐ・Ｓで計算できる。例えば、開口部の面積Ｓが1cm2で、吸盤の剛性が無限大で、シーリング機能が100％と仮定した場合、体積変化が全体の1％であるとすると、内容物が水の場合は、約200kgfの力で吸着可能となる。一方、内容物が空気の場合は、約13gfと僅かな吸着力しか発生しない。 Regarding the above bulk modulus K, the volume modulus K of water (1 atm, 20 ° C.) is 2.06 × 10 9 (Pa), and the volume modulus K of air (1 atm) is 1.4 × 10 5 (Pa). is there. Therefore, water has a bulk modulus K that is 15,000 times that of air, and produces a large negative pressure with a minute volume change compared to air, thus exhibiting a large suction cup effect. Here, the suction force F generated at the opening of the suction cup can be calculated by dp · S, where S is the area of the opening. For example, assuming that the area S of the opening is 1 cm 2 , the suction cup rigidity is infinite, the sealing function is 100%, and the volume change is 1% of the whole, Adsorption is possible with a force of about 200kgf. On the other hand, when the contents are air, only a slight adsorption force of about 13 gf is generated.
上述のように、開口部の面積Ｓが1cm2で、吸盤の剛性が無限大で、シーリング機能が100％と仮定した場合、体積変化が全体の1％であるとすると、内容物が水の場合は、約200kgfの力で吸着可能となるが、実際には、物体の剛性は無限大ではないため、微小変形することで実際の体積変化が小さくなり、また、シーリング部からの漏れ等で実際にはかかる大きな吸着力は発生しない。従って、吸着力を向上させるためには、これらの点を改良すべく、以下の三点に留意する必要である。 As described above, assuming that the opening area S is 1 cm 2 , the suction cup rigidity is infinite, and the sealing function is 100%, assuming that the volume change is 1% of the whole, the contents are water. In this case, it can be adsorbed with a force of about 200 kgf, but in reality the rigidity of the object is not infinite, so the actual volume change will be small by small deformation, and leakage from the sealing part etc. Actually, such a large adsorption force is not generated. Therefore, in order to improve the attractive force, it is necessary to pay attention to the following three points in order to improve these points.
（１）閉空間を形成する壁面は、負圧に耐えられるだけの剛性を有する材質及び構造であることが好ましい。
（２）閉空間を形成するために、平面と物体の壁面間に液体に対するシーリング機能を持たせることが好ましい。
（３）閉空間の大きさが小さい場合、閉空間内に液体を導入するには、閉空間を形成する壁面は、内面の濡れ性が大きいことが好ましい。
(1) The wall surface forming the closed space is preferably made of a material and a structure having rigidity sufficient to withstand negative pressure.
(2) In order to form a closed space, it is preferable to provide a liquid sealing function between the plane and the wall surface of the object.
(3) When the size of the closed space is small, in order to introduce liquid into the closed space, the wall surface forming the closed space preferably has high wettability on the inner surface.
上記（１）に対して、閉空間を形成する壁面の剛性を保つためには、閉空間内の液体の体積弾性率よりも高い体積弾性率を有する材質で閉空間を形成する壁面を構成することが好ましい。従って、閉空間内の液体が水の場合は、2000MPa以上の体積弾性率Ｋを有する材料で壁面を構成することが好ましい。また、閉空間内の液体を外部に放出するためには、外力Ｆによって、体積がｄｖ相当分は変形する必要があるので、物体を断面積Ｓのシリンダー構造と仮定した場合、物体の剛性Ｍは、下記式(II)：
Ｆ＞Ｍ・（ｄｖ／ｖ）・ｈ ・・・ (II)
で表わされる関係を維持する必要がある。ここで、ｈは、物体の高さである。また、壁面部が平面と接触している面積Ｓ'が全体の構造を支えていると仮定すると、壁面材料のせん断弾性率Ｇは、使用条件で以下の式(III)：
Ｆ＞Ｇ・（ｄｖ／ｖ）・Ｓ' ・・・ (III)
を満たす必要がある。例えば、外力Ｆ＝10kgf、Ｓ'＝1cm2、体積変化＝1％とした場合は、せん断弾性率Ｇが100MPa以下の材料を用いる必要がある。以上の点から、閉空間を形成する壁面を構成する材料としては、充填剤を配合したゴム組成物が好適である。但し、1％の体積変化で、1cm2当り200kgfの力が発生することから、壁面はこの力に耐えられるだけの剛性が必要となる。このためには、1000MPa以上のせん断弾性率Ｇを有する材料で壁面の内面を構成することが好ましい。
In contrast to the above (1), in order to maintain the rigidity of the wall surface forming the closed space, the wall surface forming the closed space is made of a material having a volume elastic modulus higher than the volume elastic modulus of the liquid in the closed space. It is preferable. Therefore, when the liquid in the closed space is water, it is preferable that the wall surface is made of a material having a bulk modulus K of 2000 MPa or more. Further, in order to discharge the liquid in the closed space to the outside, it is necessary to deform the volume corresponding to dv by the external force F. Therefore, assuming that the object has a cylinder structure with a cross-sectional area S, the rigidity M of the object Is the following formula (II):
F> M · (dv / v) · h (II)
It is necessary to maintain the relationship expressed by Here, h is the height of the object. Further, assuming that the area S ′ where the wall surface portion is in contact with the flat surface supports the entire structure, the shear modulus G of the wall surface material is expressed by the following equation (III):
F> G · (dv / v) · S '(III)
It is necessary to satisfy. For example, when the external force F = 10 kgf, S ′ = 1 cm 2 , and volume change = 1%, it is necessary to use a material having a shear elastic modulus G of 100 MPa or less. From the above points, a rubber composition containing a filler is suitable as a material constituting the wall surface forming the closed space. However, since a force of 200 kgf per 1 cm 2 is generated with a volume change of 1%, the wall surface needs to be rigid enough to withstand this force. For this purpose, the inner surface of the wall surface is preferably made of a material having a shear elastic modulus G of 1000 MPa or more.
また、上記（２）に対して、平面との密着性を達成するためには、使用環境条件において、柔らかい材料を使用する必要がある。更に、横方向に物体が滑らないようにするためには、高い摩擦係数μを有する材料を使用することが好ましい。ここで、横方向で発生し得る摩擦力は、下記式(IV)：
Ｆ＝μ・ｄｐ・Ｓ ・・・ (IV)
で計算できる。最も滑り易い平面として水膜の存在する氷の表面では、ゴムでも摩擦係数μは0.01になってしまうが、体積変化1％で約200kgfの吸着力を発生させられれば、1cm2当り約2kgfの力を発生させることが可能となる。従って、シーリング部には、使用条件下でゴム状態にある材料を使用することが好ましい。なお、使用する材料のせん断弾性率Ｇは、1〜10MPaの範囲が好ましい。
In addition, in order to achieve adhesion to a plane with respect to (2) above, it is necessary to use a soft material under the usage environment conditions. Further, in order to prevent the object from slipping in the lateral direction, it is preferable to use a material having a high coefficient of friction μ. Here, the frictional force that can be generated in the lateral direction is expressed by the following formula (IV):
F = μ · dp · S (IV)
It can be calculated with On the surface of ice with a water film as the most slippery plane, the friction coefficient μ is 0.01 even with rubber, but if an adsorption force of about 200 kgf can be generated with a volume change of 1%, about 2 kgf per cm 2 Force can be generated. Therefore, it is preferable to use a material that is in a rubber state under use conditions for the sealing portion. The shear modulus G of the material used is preferably in the range of 1 to 10 MPa.
以上の二点から、閉空間を形成する壁面を構成する材料として、加硫ゴムが最適と考えられる。これまで、閉空間を有する加硫ゴム、即ち、独立気泡を含む発泡ゴムとして種々の発泡体が知られているが、従来の発泡ゴムは、独立気泡が疎水性の材料で囲まれているため、独立気泡内面の濡れ性が小さく、上記（３）の点で問題があり、結果として、独立気泡内に水が入り難く、水による負圧が十分に発生しない。この点に関して、本発明者は、以下のように、更に検討を進めた。 From the above two points, vulcanized rubber is considered to be optimal as a material constituting the wall surface forming the closed space. Until now, various foams have been known as vulcanized rubber having a closed space, that is, foamed rubber containing closed cells, but conventional foamed rubber has closed cells surrounded by a hydrophobic material. The wettability of the inner surface of the closed cell is small, and there is a problem in the above point (3). As a result, it is difficult for water to enter the closed cell, and the negative pressure due to water is not sufficiently generated. In this regard, the present inventor further studied as follows.
上記（３）に対して、固体表面が濡れるための条件は、表面エネルギーγと接触角θの関数として、下記式(V)：
γs＞（γL・cosθ＋γSL） ・・・ (V)
で与えられる。式(V)から、γsが大きければ、接触角や液体の種類によらず、濡れ性が良くなることが分かる。表１に、各種ポリマー材料のγsを示す。
In contrast to the above (3), the condition for the solid surface to get wet is expressed by the following equation (V) as a function of the surface energy γ and contact angle θ:
γ s > (γ L・ cos θ + γ SL ) (V)
Given in. From formula (V), it can be seen that if γ s is large, the wettability is improved regardless of the contact angle and the type of liquid. Table 1 shows γ s of various polymer materials.
従来の発泡ゴムをトレッドに具えたスタッドレスタイヤは、独立気泡が加硫ゴムで囲まれていたり、或いは、独立気泡がポリエチレン層で囲まれており、γsが大きくないため、濡れ性が悪く、結果として、独立気泡内に水が入り難かった。この場合、独立気泡内に占める水の割合が低下し、空気の割合が上昇するため、押圧により排出される流体の体積弾性率が低い上、押圧により排出される水の量も少なかった。この点を改善すべく、本発明者は、独立気泡を含み、該独立気泡が表面層で囲まれている発泡ゴムにおいて、該独立気泡を囲む表面層に親水性を持たせることを想到した。 Studless tires with conventional foam rubber in the tread have closed cells surrounded by vulcanized rubber, or closed cells are surrounded by a polyethylene layer, γ s is not large, so wettability is bad, As a result, it was difficult for water to enter the closed cells. In this case, since the proportion of water in the closed cells decreases and the proportion of air increases, the volume elastic modulus of the fluid discharged by pressing is low and the amount of water discharged by pressing is small. In order to improve this point, the present inventor has conceived that in a foamed rubber containing closed cells and surrounded by a surface layer, the surface layer surrounding the closed cells is made hydrophilic.
上述の吸盤の理論に基づくと、独立気泡を含んだ発泡ゴムを、路面に押し当てた際の発泡ゴムの吸着力は、以下の式(VI)：
吸着力∝Ｆ（体積弾性率、水の排出量） ・・・ (VI)
で表わされる。そして、本発明に従って、独立気泡を親水性の表面層で囲むことで、独立気泡内に水が入り込み易くなり、押圧により排出される流体の体積弾性率が向上すると共に、予め水が独立気泡内に入り込んでいるため、水の排出量も大きくなる。そして、これらの効果により、氷雪路面等の平滑面に対する発泡ゴムの吸着力が大幅に向上する。
Based on the suction cup theory described above, the adsorbing force of the foam rubber when the foam rubber containing closed cells is pressed against the road surface is expressed by the following formula (VI):
Adsorption power ∝F (volume modulus, water discharge) (VI)
It is represented by Then, according to the present invention, by surrounding the closed cells with a hydrophilic surface layer, water can easily enter the closed cells, the volume elastic modulus of the fluid discharged by pressing is improved, and the water is previously contained in the closed cells. The amount of water discharged is also large. And by these effects, the adsorption | suction power of foamed rubber with respect to smooth surfaces, such as an ice-snow road surface, improves significantly.
なお、発泡ゴムに負圧を発生させるためには、外圧により発泡ゴム内から微小体積の液体を外部に排出する機能が必要となるが、この点に対しては、力積の原理に基づき、一定のエネルギーを短時間で与え、大きな力を瞬間的に発生させることで、発泡ゴム内の液体を外部に排出することが可能となる。例えば、タイヤのトレッドに適用する場合には、路面にトレッド表面が接触する踏み込み部で発生する急激な圧力上昇を利用して、濡れた平滑面での吸着効果が得られる。 In addition, in order to generate a negative pressure in the foam rubber, a function of discharging a minute volume of liquid from the foam rubber to the outside by the external pressure is necessary, but this point is based on the principle of impulse. By applying a constant energy in a short time and generating a large force instantaneously, the liquid in the foamed rubber can be discharged to the outside. For example, when applied to a tread of a tire, an absorptive effect on a wet smooth surface can be obtained by utilizing a sudden pressure increase generated at a stepped portion where the tread surface contacts the road surface.
独立気泡２を囲む表面層３に親水性を持たせるには、独立気泡を囲む表面層３が極性基を有することが好ましく、該極性基は、親水性の観点から、水素結合能を有することが好ましい。ここで、該極性基としては、水酸基、カルボン酸基、スルホン酸基、リン酸基等のイオン性官能基の他、エステル基、スルフォン基、アミド基等が挙げられる。これらの中でも、イオン性官能基が好ましい。
In order to make the
また、上記独立気泡２を囲む表面層３は、高い親水性を有する点で、イオン性ポリマーからなることが好ましい。ここで、イオン性ポリマーとしては、エチレン-メタアクリル酸共重合体、エチレン-アクリル酸共重合体、スチレン-メタアクリル酸共重合体、スルホン化ポリスチレン、ポリビニルピリジウム塩、ポリビニルトリメチルアンモニウム塩、ポリビニルベンジルホスホニウム塩、ポリウレタンアイオノマー等が挙げられる。
The
また、独立気泡がポリエチレン皮膜で囲まれた発泡ゴムよりも高い吸着力を発現させる観点から、上記表面層３の表面エネルギーは、30mJ/m2以上であることが好ましい。
Further, from the viewpoint of expressing higher adsorbing power than foamed rubber in which closed cells are surrounded by a polyethylene film, the surface energy of the
本発明の発泡ゴムは、例えば、ゴム成分に、イオン性ポリマー等の親水性化合物、発泡剤等を配合し、ロール、インターナルミキサー等の混練り機を用いて混練りすることによってゴム組成物を調製し、該ゴム組成物を所望の形状に成形加工した後、加硫することで作製することができる。なお、ゴム組成物の加硫工程において、発泡剤により加硫ゴム中に独立気泡が形成されて、発泡ゴムとなる。ここで、親水性化合物は、親水性であるため、ゴムとの相溶性が低く、ゴムマトリックス側から加硫中に生成する独立気泡側へ移動して、表面に析出し、独立気泡を囲むこととなる。従って、独立気泡２を囲む表面層３を形成する材料（親水性化合物）の融点は、加硫中に溶融・分散するために、200℃以下であることが好ましく、190℃以下であることが更に好ましく、180℃以下であることが特に好ましい。なお、分散が悪いと、ゴム組成物中に補強されていない異物として残ることになるため、破壊核となり、破壊強力が低下する。
The foamed rubber of the present invention is, for example, a rubber composition obtained by blending a rubber component with a hydrophilic compound such as an ionic polymer, a foaming agent, and the like, and kneading using a kneader such as a roll or an internal mixer. After the rubber composition is prepared, the rubber composition is molded into a desired shape and then vulcanized. In the vulcanization process of the rubber composition, closed cells are formed in the vulcanized rubber by the foaming agent to form foamed rubber. Here, since the hydrophilic compound is hydrophilic, the compatibility with the rubber is low, and it moves from the rubber matrix side to the closed cell side generated during vulcanization, precipitates on the surface, and surrounds the closed cell. It becomes. Therefore, the melting point of the material (hydrophilic compound) that forms the
上記親水性化合物としては、上記イオン性ポリマーの他に、ポリオキシエチレン等が挙げられる。なお、該親水性化合物のせん断弾性率Ｇは、ゴムマトリクスのせん断弾性率Ｇよりも大きいことが好ましく、この場合、独立気泡の体積弾性率Ｋが増大し、吸着力が大きくなる。 Examples of the hydrophilic compound include polyoxyethylene in addition to the ionic polymer. The shear modulus G of the hydrophilic compound is preferably larger than the shear modulus G of the rubber matrix. In this case, the volume modulus K of closed cells increases and the adsorption force increases.
上記発泡ゴム用ゴム組成物に用いるゴム成分としては、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）等が挙げられる。これらゴム成分は、一種単独で使用してもよいし、二種以上を組み合わせて使用してもよい。 Examples of the rubber component used in the rubber composition for foamed rubber include natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR) and the like. These rubber components may be used individually by 1 type, and may be used in combination of 2 or more type.
上記発泡ゴム用ゴム組成物に用いる発泡剤としては、ジニトロソペンタメチレンテトラミン（ＤＮＰＴ）、アゾジカルボンアミド（ＡＤＣＡ）、ジニトロソペンタスチレンテトラミンやベンゼンスルホニルヒドラジド誘導体、ｐ,ｐ'-オキシビスベンゼンスルホニルヒドラジド（ＯＢＳＨ）、二酸化炭素を発生する重炭酸アンモニウム、重炭酸ナトリウム、炭酸アンモニウム、窒素を発生するニトロソスルホニルアゾ化合物、Ｎ,Ｎ'-ジメチル-Ｎ,Ｎ'-ジニトロソフタルアミド、トルエンスルホニルヒドラジド、ｐ-トルエンスルホニルセミカルバジド、ｐ,ｐ'-オキシビスベンゼンスルホニルセミカルバジド等が挙げられる。これら発泡剤は、一種単独で使用してもよいし、二種以上を併用してもよい。また、該発泡剤には、発泡助剤として尿素、ステアリン酸亜鉛、ベンゼンスルフィン酸亜鉛や亜鉛華等を併用することが好ましい。 Examples of the foaming agent used in the rubber composition for foamed rubber include dinitrosopentamethylenetetramine (DNPT), azodicarbonamide (ADCA), dinitrosopentastyrenetetramine, benzenesulfonylhydrazide derivatives, and p, p′-oxybisbenzenesulfonyl. Hydrazide (OBSH), ammonium bicarbonate generating carbon dioxide, sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound generating nitrogen, N, N'-dimethyl-N, N'-dinitrosophthalamide, toluenesulfonylhydrazide , P-toluenesulfonyl semicarbazide, p, p′-oxybisbenzenesulfonyl semicarbazide and the like. These foaming agents may be used individually by 1 type, and may use 2 or more types together. The foaming agent is preferably used in combination with urea, zinc stearate, zinc benzenesulfinate, zinc white or the like as a foaming aid.
なお、本発明の発泡ゴムに用いるゴム組成物には、本発明の目的を損なわない範囲で、カーボンブラックやシリカ等の充填剤、シランカップリング剤、軟化剤、加硫剤、加硫促進剤、老化防止剤、酸化亜鉛、ステアリン酸等の通常ゴム業界で用いられ各種配合剤を適宜配合することができる。 The rubber composition used for the foamed rubber of the present invention includes fillers such as carbon black and silica, silane coupling agents, softeners, vulcanizing agents, and vulcanization accelerators as long as the object of the present invention is not impaired. Various compounding agents which are usually used in the rubber industry such as anti-aging agent, zinc oxide and stearic acid can be appropriately blended.
本発明のタイヤは、トレッドゴムとして上述した発泡ゴムを具えることを特徴とする。本発明のタイヤは、減圧吸盤吸着理論に基づく発泡ゴムをトレッド部に具えるため、氷雪路面等の滑り易い路面上においても優れたグリップ性能を発揮し、スタッドレスタイヤとして好適に使用できる。本発明のタイヤは、例えば、発泡ゴム用の未加硫ゴム組成物をトレッドゴムとして用いて生タイヤを作製した後、該生タイヤを加硫することで製造できる。 The tire of the present invention is characterized by including the above-described foamed rubber as a tread rubber. Since the tire of the present invention includes foam rubber based on the suction suction suction theory in the tread portion, it exhibits excellent grip performance even on slippery road surfaces such as icy and snowy road surfaces, and can be suitably used as a studless tire. The tire of the present invention can be produced, for example, by producing a raw tire using an unvulcanized rubber composition for foam rubber as a tread rubber, and then vulcanizing the raw tire.
また、本発明の靴は、靴底として上述した発泡ゴムを具えることを特徴とする。本発明の靴は、減圧吸盤吸着理論に基づく発泡ゴムを靴底に具えるため、氷雪路面等の滑り易い路面上においても滑り難く、安全な歩行を可能とする。本発明の靴は、例えば、上述した発泡体からなる所望の形状の靴底を作製し、該靴底を別途作製した靴の靴底以外の部分に貼付することで製造できる。 The shoe of the present invention is characterized by comprising the above-described foamed rubber as a shoe sole. Since the shoe of the present invention has foam rubber based on the suction suction suction theory on the shoe sole, it is difficult to slip even on slippery road surfaces such as icy and snowy road surfaces and enables safe walking. The shoe of the present invention can be produced, for example, by producing a shoe sole having a desired shape made of the above-mentioned foam and attaching the shoe sole to a portion other than the shoe sole of the shoe produced separately.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
上述の理論を実証するために、表２に示すポリマーを用い、モデル試験片を以下の手順で作製した。なお、本試験では、シーリング部は外側を囲うゴム片にその機能を持たせた。 In order to verify the above theory, a model test piece was prepared by the following procedure using the polymers shown in Table 2. In this test, the sealing part was given the function to the rubber piece surrounding the outside.
１．表面に突起を有する金属モールドを作製した。なお、突起の高さは、100μmとした。
２．金属モールドの上に表２に示したポリマーの薄膜を溶媒キャスティング法により形成した。
３．金属モールド上に、未加硫ゴム組成物を配置し、145℃で、33分間加硫を行った。
４．金属モールド表面の突起パターンが転写された加硫ゴムの表面をミクロトームでスライスした。なお、凹部の深さは、30μmとした。
1. A metal mold having protrusions on the surface was produced. The height of the protrusion was 100 μm.
2. A polymer thin film shown in Table 2 was formed on a metal mold by a solvent casting method.
3. An unvulcanized rubber composition was placed on a metal mold and vulcanized at 145 ° C. for 33 minutes.
4). The surface of the vulcanized rubber onto which the protrusion pattern on the metal mold surface was transferred was sliced with a microtome. The depth of the recess was 30 μm.
次に、上記モデル試験片を、水膜の存在する平滑面（0℃付近の氷表面）に一定荷重Ｆで押し付け、約0.1秒後に引き剥がし力をロードセルによって計測し、吸着力とした。結果は、ポリエチレンの吸着力を100として、指数表示した。 Next, the model test piece was pressed against a smooth surface (ice surface near 0 ° C.) where a water film was present with a constant load F, and after about 0.1 second, the peeling force was measured with a load cell to obtain an adsorption force. The results are expressed as an index with the adsorption power of polyethylene as 100.
表２から明らかなように、表面エネルギーγsの大きなポリマー、即ち、親水性のポリマーを使用することで、吸着力が大きくなることが確認できた。 As is apparent from Table 2, it was confirmed that the adsorption force was increased by using a polymer having a large surface energy γ s , that is, a hydrophilic polymer.
次に、表３及び表４に示す配合処方のゴム組成物を調製し、該ゴム組成物をトレッドゴムとして用いた、サイズ１９５／６０Ｒ１５のスタッドレスタイヤを試作した。また、該タイヤに対して、氷上制動試験を行い、ブレーキ停止距離を測定し、比較例５のタイヤの停止距離の逆数を100として指数表示した。指数値が大きい程、停止距離が短く、氷上性能に優れることを示す。また、トレッドゴムの破壊強力をＪＩＳ Ｋ６２５１に従って測定し、比較例４を100として指数表示した。指数値が大きい程、破壊強力が高く、良好であることを示す。結果を表３及び表４に示す。また、使用したポリマーの表面エネルギー及び融点を表５に示す。 Next, rubber compositions having the formulation shown in Tables 3 and 4 were prepared, and a size 195 / 60R15 studless tire using the rubber composition as a tread rubber was manufactured as a prototype. In addition, an on-ice braking test was performed on the tire, and the brake stop distance was measured. The larger the index value, the shorter the stopping distance and the better the performance on ice. Further, the breaking strength of the tread rubber was measured according to JIS K6251 and indicated as an index with Comparative Example 4 being 100. The larger the index value, the higher the breaking strength and the better. The results are shown in Tables 3 and 4. Table 5 shows the surface energy and melting point of the polymer used.
*1 宇部興産社製, ＵＢＥＰＯＬ １５０Ｌ
*2 旭カーボン社製, Ｎ１３４, Ｎ2ＳＡ＝142m2/g
*3 日本シリカ社製, Ｎｉｐｓｉｌ ＡＱ
*4 デグッサ社製, Ｓｉ６９
*5 Ｎ-イソプロピル-Ｎ'-フェニル-ｐ-フェニレンジアミン
*6 ジベンゾチアジルジスルフィド
*7 Ｎ-シクロヘキシル-２-ベンゾチアゾールスルフェンアミド
*8 ジニトロソペンタメチレンテトラミン
*9 三井デュポンクロロケミカル社製
*10 旭化成社製
*11 ＪＳＲ社製
*12 旭化成社製
*13 旭化成社製
*14 住友化学社製
*15 出光石油化学社製
*16 旭化成社製
*17 住友化学社製
*18 三井化学社製
*19 日産化学社製
*20 三井化学社製
* 1 Ube Industries, UBEPOL 150L
* 2 Asahi Carbon Co., Ltd., N134, N 2 SA = 142m 2 / g
* 3 Nippon Silica, Nippon AQ
* 4 Degussa, Si69
* 5 N-isopropyl-N'-phenyl-p-phenylenediamine
* 6 Dibenzothiazyl disulfide
* 7 N-cyclohexyl-2-benzothiazolesulfenamide
* 8 Dinitrosopentamethylenetetramine
* 9 Made by Mitsui DuPont Chloro Chemical Co., Ltd.
* 10 Asahi Kasei Corporation
* 11 JSR made
* 12 Asahi Kasei Corporation
* 13 Asahi Kasei Corporation
* 14 Made by Sumitomo Chemical
* 15 Made by Idemitsu Petrochemical Co., Ltd.
* 16 Asahi Kasei
* 17 Made by Sumitomo Chemical
* 18 Mitsui Chemicals
* 19 Nissan Chemical Co., Ltd.
* 20 Made by Mitsui Chemicals
表３及び表４から、トレッドに用いる発泡ゴム用のゴム組成物にリニアポリエチレンよりも表面エネルギーγsが大きい材料を配合することで、タイヤの氷上性能が向上することが確認できた。 From Table 3 and Table 4, it has confirmed that the on-ice performance of a tire improved by mix | blending the material whose surface energy (gamma) s is larger than a linear polyethylene with the rubber composition for foaming rubbers used for a tread.
１ 発泡ゴム
２ 独立気泡
３ 表面層
1
Claims (9)
前記独立気泡を囲む表面層が親水性を有することを特徴とする発泡ゴム。 In foamed rubber containing closed cells, the closed cells being surrounded by a surface layer,
A foamed rubber characterized in that a surface layer surrounding the closed cells has hydrophilicity.
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| WO2016076432A1 (en) * | 2014-11-14 | 2016-05-19 | 株式会社アシックス | Outer sole and shoes |
| US9392841B2 (en) | 2014-08-27 | 2016-07-19 | Nike Innovate C.V. | Article of footwear with soil-shedding performance |
| JP2018021111A (en) * | 2016-08-02 | 2018-02-08 | 株式会社ブリヂストン | Rubber member and tire |
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