JP2015105442A - Fiber for reinforcement of rubber structure and method for producing the same - Google Patents
Fiber for reinforcement of rubber structure and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、カーボンナノチューブ（以下「ＣＮＴ」という）を分散させたゴム構造体補強用繊維及びその製造方法に関する。 The present invention relates to a fiber for reinforcing a rubber structure in which carbon nanotubes (hereinafter referred to as “CNT”) are dispersed, and a method for producing the same.
タイヤコードなどのゴム構造体を補強するための繊維（以下「ゴム構造体補強用繊維」という）として、以前は天然繊維であるセルロース繊維が多く用いられていた。しかしその後、高強度のナイロンや、さらにこれに加えて高弾性率であるという特徴を有するポリエステルなど、ゴム構造体補強用繊維に求められる優れた特性を備えた合成繊維が出現し、セルロース繊維はこれらの繊維にとって代わられつつあった。 As fibers for reinforcing rubber structures such as tire cords (hereinafter referred to as “fibers for reinforcing rubber structures”), cellulose fibers that are natural fibers have been used in many cases. However, after that, synthetic fibers with excellent properties required for rubber structure reinforcing fibers, such as high-strength nylon and polyester having a high elastic modulus in addition to this, emerged. These fibers were being replaced.
ところが、ナイロン、ポリエステルなどの合成繊維は、熱で溶けやすいという欠点を有している。例えばこれらの繊維をタイヤコードに用いた場合、高速走行時などにタイヤが摩擦などによって高温で発熱すると、タイヤコードが溶けて自動車が急停止してしまい、大事故につながりかねないといった問題がある。これに対し、セルロース繊維であれば、タイヤの発熱により炭化して固まることはあっても溶けてしまうことはないので、発熱後一定時間はタイヤの構造を保持しつつタイヤの受ける荷重、衝撃などに耐えるための最低限の機能を保つことができる。このため、その間に自動車を安全な場所まで移動することができ、大事故を未然に防ぐことができる。 However, synthetic fibers such as nylon and polyester have a drawback that they are easily melted by heat. For example, when these fibers are used in tire cords, there is a problem that if the tire generates heat at a high temperature due to friction or the like when driving at high speed, the tire cord melts and the vehicle suddenly stops, which may lead to a major accident. . On the other hand, if it is cellulose fiber, it will not melt even if it is carbonized due to heat generation of the tire, so it will not melt, so the load that the tire receives, impact etc. while holding the tire structure for a certain time after heat generation Can keep the minimum function to withstand. For this reason, the automobile can be moved to a safe place in the meantime, and a major accident can be prevented.
こうしたことから、ゴム構造体補強用繊維としてのセルロース繊維の有用性が改めて見直され、セルロース繊維は上述の合成繊維に完全にとって代わられることなく、依然として使われ続けているという現状にある。 For these reasons, the usefulness of cellulose fibers as rubber structure reinforcing fibers has been reviewed again, and the cellulose fibers are still being used without being completely replaced by the synthetic fibers described above.
その一方で、セルロース繊維を高強度、高弾性率のものにする工夫もなされている。こうした繊維として、例えばＣＮＴを含有したセルロース繊維が知られており、その一例として、特許文献１には、塩及びポリビニルアルコールを溶解させたＮＭＭＯ（Ｎ−メチルモルホリン−Ｎ−オキシド）溶液と、ＣＮＴを混合したセルロース粉末とを混合、膨潤及び溶解させ、湿式紡糸法を用いて紡糸することにより製造されるセルロース繊維が開示されている（特許文献１参照）。しかしながら、ゴム構造体補強用繊維については、これまでＣＮＴを含有したセルロース繊維を用いたものは知られていなかった。 On the other hand, the device which makes a cellulose fiber the thing of high intensity | strength and a high elastic modulus is also made | formed. As such fibers, for example, cellulose fibers containing CNT are known. As an example, Patent Document 1 discloses an NMMO (N-methylmorpholine-N-oxide) solution in which a salt and polyvinyl alcohol are dissolved, and CNT. A cellulose fiber produced by mixing, swelling, and dissolving cellulose powder mixed with selenium and spinning using a wet spinning method is disclosed (see Patent Document 1). However, as a rubber structure reinforcing fiber, a fiber using CNT-containing cellulose fiber has not been known so far.
ところで、セルロース繊維を用いたゴム構造体補強用繊維を用いたゴム構造体の製造工程においても、他のゴム構造体補強用繊維を用いたゴム構造体の製造工程におけるのと同様に、加硫処理が行われるのが一般である。加硫処理は、ゴム系の原材料を加工してゴム構造体を製造する際に、ゴムに硫黄などの加硫剤を加え、高温蒸熱処理によってゴムを強化する処理である。しかしながら、セルロース繊維は吸水性が高く２０℃、６５％の湿度下で約１２から１４％の水を含んでいる。そこで、加硫処理における高温蒸着処理によってセルロース繊維の非晶質部分に入り込んでいる水が高温になると、セルロース繊維を形成している分子が切れやすくなり、この結果、製造されるゴム構造体の力学的な特性が劣化するという問題がある。 By the way, in the manufacturing process of a rubber structure using a fiber for reinforcing a rubber structure using cellulose fibers, as in the manufacturing process of a rubber structure using another fiber for reinforcing a rubber structure, vulcanization is performed. Generally, processing is performed. The vulcanization treatment is a treatment for reinforcing a rubber by high-temperature steaming heat treatment by adding a vulcanizing agent such as sulfur to the rubber when a rubber-based raw material is processed to produce a rubber structure. However, cellulose fibers are highly water absorbent and contain about 12-14% water at 20 ° C. and 65% humidity. Therefore, when the water entering the amorphous part of the cellulose fiber is heated to a high temperature by the high temperature vapor deposition process in the vulcanization process, the molecules forming the cellulose fiber are easily cut. As a result, the rubber structure produced There is a problem that the mechanical characteristics deteriorate.
しかしながら、これまで、セルロース繊維を用いたゴム構造体補強用繊維の分野において、このような加硫処理における高温蒸着処理によってゴム構造体の力学的な特性が劣化するという課題は解決されてこなかったところである。 However, until now, in the field of rubber structure reinforcing fibers using cellulose fibers, the problem that the mechanical properties of the rubber structure deteriorate due to such high-temperature vapor deposition in vulcanization has not been solved. By the way.
本発明はこのような問題点に鑑みたものである。即ち、本発明の発明者は、ＣＮＴ含有セルロース繊維を用いたゴム構造体補強用繊維について、セルロースにＣＮＴを分散させることでセルロース繊維の結晶部分を増やしたＣＮＴ含有繊維を適用することにより、力学的特性に寄与する結晶部分は非晶質部分に比べ緻密で結晶間に水分など他の物質が入りにくいことにより、劣化の影響を受けにくくかつまた加硫中あるいは使用時の劣化を抑制できることを見出し、ゴム構造体の力学的な特性の劣化を防止するという発想に至った。本発明が解決すべき課題は、ＣＮＴを含有させて結晶性が高いセルロース繊維をゴム構造体補強用繊維に用いるものであり、特に、加硫処理に際してゴム構造体の力学的特性を劣化させにくくかつ使用後の経時劣化の少ないゴム構造体補強用繊維を提供し、また、このようなゴム構造体補強用繊維の製造方法を提供することにある。 The present invention has been made in view of such problems. That is, the inventor of the present invention applied a CNT-containing fiber in which the crystal portion of the cellulose fiber was increased by dispersing the CNT in cellulose to the rubber structure reinforcing fiber using the CNT-containing cellulose fiber. The crystal part that contributes to the mechanical properties is denser than the amorphous part, and other substances such as moisture are less likely to enter between crystals, making it less susceptible to deterioration and suppressing deterioration during vulcanization or use. The inventor came up with the idea of preventing the deterioration of the mechanical properties of the rubber structure. The problem to be solved by the present invention is that cellulose fibers containing CNTs and having high crystallinity are used as fibers for reinforcing rubber structures, and in particular, the mechanical properties of the rubber structures are hardly deteriorated during vulcanization treatment. Another object of the present invention is to provide a rubber structure reinforcing fiber with little deterioration with time after use, and to provide a method for producing such a rubber structure reinforcing fiber.
以上の課題を解決するため、本発明のうち、第一の発明は、セルロース中にＣＮＴを分散することでＣＮＴが分散されていないセルロースよりも結晶性を向上させたゴム構造体補強用繊維を提供する。 In order to solve the above problems, among the present invention, the first invention is a rubber structure reinforcing fiber having improved crystallinity compared to cellulose in which CNT is not dispersed by dispersing CNT in cellulose. provide.
また、第二の発明は、第一の発明を基礎として、結晶化度が６０％以上、結晶配向度が０．８５以上であるゴム構造体補強用繊維を提供する。 The second invention provides a fiber for reinforcing a rubber structure having a crystallinity of 60% or more and a crystal orientation of 0.85 or more on the basis of the first invention.
また、第三の発明は、第一又は第二の発明を基礎として、引っ張り強度が１ＧＰａ以上であり、初期引っ張り弾性率が５０ＧＰａ以上であり、かつ乾熱収縮率が−０．２％以上であるゴム構造体補強用繊維を提供する。 The third invention is based on the first or second invention, has a tensile strength of 1 GPa or more, an initial tensile elastic modulus of 50 GPa or more, and a dry heat shrinkage of -0.2% or more. A rubber structure reinforcing fiber is provided.
また、第四の発明は、第一から第三のいずれか一の発明を基礎として、高温飽和水蒸気処理後の強力保持率が９０％以上であるゴム構造体補強用繊維を提供する。 Moreover, 4th invention provides the fiber for rubber structure reinforcement which is 90% or more of the strong retention after high temperature saturated steam processing on the basis of any one invention of 1st to 3rd.
また、第五の発明は、第一から第四のいずれか一に記載の発明を基礎として、ＣＮＴ含有量がセルロース繊維に対して０．００５重量％以上１重量％以下であるゴム構造体補強用繊維を提供する。 Further, the fifth invention is based on the invention according to any one of the first to fourth aspects, wherein the CNT content is 0.005 wt% to 1 wt% with respect to the cellulose fiber. Provide fiber for use.
また、第六の発明は、第一から第五のいずれか一の発明にかかるゴム構造体補強用繊維の製造方法であって、繊維原料に混練されるＣＮＴは、平均直径（Ａｖ）と直径分布（３σ）とが０．６０>３σ／Ａｖ>０．２０という条件を満たすＣＮＴを用いるゴム構造体補強用繊維の製造方法を提供する。 A sixth invention is a method for producing a fiber for reinforcing a rubber structure according to any one of the first to fifth inventions, wherein the CNT kneaded in the fiber raw material has an average diameter (Av) and a diameter. Provided is a method for producing a fiber for reinforcing a rubber structure using CNTs whose distribution (3σ) satisfies the condition of 0.60> 3σ / Av> 0.20.
また、第七の発明は、第六の発明を基礎として、分子量が２００以上８００以下のセルロース繊維を原料に用いるゴム構造体補強用繊維の製造方法を提供する。 Moreover, 7th invention provides the manufacturing method of the fiber for rubber structure reinforcement which uses the cellulose fiber whose molecular weight is 200-800 as a raw material on the basis of 6th invention.
本発明により、ＣＮＴ含有セルロース繊維からなるゴム構造体補強用繊維であって、加硫処理に際してゴム構造体の力学的特性を劣化させにくくかつ使用後の経時劣化の少ないゴム構造体補強用繊維を提供することが可能となる。また、このようなゴム構造体補強用繊維の製造方法を提供することが可能となる。 According to the present invention, there is provided a rubber structure reinforcing fiber composed of CNT-containing cellulose fibers, which hardly deteriorates the mechanical properties of the rubber structure during vulcanization and has little deterioration with time after use. It becomes possible to provide. It is also possible to provide a method for producing such a rubber structure reinforcing fiber.
以下に、本発明の実施例を説明する。なお、本発明はこの実施例に何ら限定されるものではなく、その要旨を逸脱しない範囲において、種々なる態様で実施しうる。 Examples of the present invention will be described below. In addition, this invention is not limited to this Example at all, and can be implemented in various modes without departing from the gist thereof.
<概要> <Overview>
本実施例のゴム構造体補強用繊維は、セルロース中にＣＮＴを分散することでＣＮＴが分散されていないセルロースよりも結晶性を向上させたゴム構造体補強用繊維である。本実施例の発明は、加硫処理におけるゴム構造体の力学的特性の劣化防止という課題を、ゴム構造体補強用繊維を構成するセルロース繊維の非晶質部分を従来のものより相対的に減らすことで結晶性を向上させることにより解決するものである。また、このような繊維であって、結晶化度が６０％以上、結晶配向度が０．８５以上であるもの、引っ張り強度が１ＧＰａ以上であり、初期引っ張り弾性率が５０ＧＰａ以上であり、かつ乾熱収縮率が−０．２％以上であるもの、高温飽和水蒸気処理後の強力保持率が９０％以上であるもの、又はＣＮＴ含有量がセルロース繊維に対して０．００５重量％以上１重量％以下であるものも本実施例の発明に含まれる。 The rubber structure reinforcing fiber of the present example is a rubber structure reinforcing fiber having improved crystallinity as compared with cellulose in which CNT is not dispersed by dispersing CNT in cellulose. In the invention of this example, the problem of preventing the deterioration of the mechanical properties of the rubber structure in the vulcanization treatment is reduced relative to the amorphous portion of the cellulose fiber constituting the rubber structure reinforcing fiber compared to the conventional one. This is solved by improving the crystallinity. Further, such a fiber having a crystallinity of 60% or more, a crystal orientation of 0.85 or more, a tensile strength of 1 GPa or more, an initial tensile elastic modulus of 50 GPa or more, and a dryness. Those having a thermal shrinkage of -0.2% or more, those having a strong retention after high-temperature saturated steam treatment of 90% or more, or CNT content of 0.005% to 1% by weight with respect to cellulose fibers The following is also included in the invention of this embodiment.
<構成> <Configuration>
（全般） (General)
本実施例のゴム構造体補強用繊維は、セルロース中にＣＮＴを分散することでＣＮＴが分散されていないセルロースよりも結晶性を向上させたゴム構造体補強用繊維である。後述する実験の結果、ＣＮＴが分散されていないセルロースよりも結晶性を向上させたゴム構造体補強用繊維とすることで、加硫処理に際してゴム構造体の力学的特性を劣化させにくいゴム構造体補強用繊維を提供するという目的を達成できることがデータによっても実証されたところであるが、このことを理論的に説明すれば、概略次のとおりである。 The rubber structure reinforcing fiber of the present example is a rubber structure reinforcing fiber having improved crystallinity as compared with cellulose in which CNT is not dispersed by dispersing CNT in cellulose. As a result of an experiment described later, a rubber structure reinforcing fiber that has improved crystallinity as compared with cellulose in which CNT is not dispersed, thereby preventing deterioration of the mechanical properties of the rubber structure during vulcanization treatment. The data has proved that the object of providing the reinforcing fiber can be achieved, but this can be explained theoretically as follows.
上述のように、セルロース繊維は、加硫処理に際してセルロース繊維を形成している分子がセルロース繊維中に存在する水分子との反応により加水分解し低分子化しやすいという問題を有している。しかしながら、セルロース繊維にＣＮＴを分散してその結晶性を向上させることで、非晶質部分の割合が相対的に減り、これに伴いセルロース繊維全体に含まれる水の割合を相対的に減らすことができるため、結晶に対する水の悪影響を減らすことができる。そこで、このようにＣＮＴを分散して結晶性を向上させたセルロース繊維をゴムと一体として加硫処理を行うことで、加硫処理に際してゴム構造体を劣化させにくくすることができるのである。 As described above, the cellulose fiber has a problem that the molecules forming the cellulose fiber during the vulcanization treatment are easily hydrolyzed by the reaction with the water molecules present in the cellulose fiber to reduce the molecular weight. However, by dispersing CNTs in cellulose fibers and improving their crystallinity, the proportion of amorphous parts is relatively reduced, and accordingly, the proportion of water contained in the whole cellulose fibers is relatively reduced. Therefore, the adverse effect of water on the crystal can be reduced. Thus, by subjecting the cellulose fibers, in which CNTs are dispersed and improved in crystallinity, to vulcanization with the rubber, the rubber structure can be made difficult to deteriorate during the vulcanization.
（ゴム構造体補強用繊維） (Fiber for reinforcing rubber structures)
ゴム構造体補強用繊維は、ゴム構造体の補強用の繊維である。「ゴム構造体」は、冒頭に述べたような問題認識に照らし、主に自動車用の部材として用いられるゴム構造体、例えば、タイヤコード、ファンベルトなどを想定しているが、これに限られるものではなく、ゴムを用いた構造体が広く含まれる。 The fiber for reinforcing the rubber structure is a fiber for reinforcing the rubber structure. The “rubber structure” is assumed to be a rubber structure mainly used as a member for automobiles, for example, a tire cord, a fan belt, etc. in light of the problem recognition described at the beginning, but is not limited thereto. It is not a thing but the structure using rubber | gum is widely included.
（セルロース繊維） (Cellulose fiber)
セルロース繊維としては、レーヨン、ポリノジックレーヨン、キュプラ、テンセル、リヨセルなどのセルロース系再生繊維や、綿、亜麻（リネン）、ラミー、バナナ、竹、ケナフ、月桃、ヘンプ、カポック等のセルロース系天然繊維のいずれも使用可能である。ただし、高強力繊維という観点からは、比較的高分子量（分子量１３００〜１４００程度）で物性の高い良質のパルプを原料とするレーヨンなどが選ばれる。一方、価格面ではサトウキビ由来のバガスなどから得られる低分子量の安価なセルロース系繊維がより適している。ここで低分子量は、好適には分子量８００以下程度をいい、より好適には分子量２００以上８００以下をいい、さらに好適には分子量４００以上８００以下をいう。これは、分子量が４００未満であると構造的に高強力という特性を保つことが困難となり、分子量が２００未満であるとこれがさらに困難となる一方、分子量が８００を超えると価格面でのメリットが減殺されるためである。 Cellulose fibers include cellulosic regenerated fibers such as rayon, polynosic rayon, cupra, tencel, and lyocell, and cellulosic natural fibers such as cotton, flax (linen), ramie, banana, bamboo, kenaf, moon peach, hemp, and kapok. Either of these can be used. However, from the viewpoint of high-strength fibers, rayon or the like made from high-quality pulp having a relatively high molecular weight (molecular weight of about 1300 to 1400) and high physical properties is selected. On the other hand, low-molecular-weight and inexpensive cellulosic fibers obtained from sugarcane-derived bagasse and the like are more suitable. Here, the low molecular weight preferably means a molecular weight of about 800 or less, more preferably a molecular weight of 200 or more and 800 or less, and further preferably a molecular weight of 400 or more and 800 or less. This is because if the molecular weight is less than 400, it is difficult to maintain the characteristic of structurally high strength, and if the molecular weight is less than 200, this becomes more difficult. On the other hand, if the molecular weight exceeds 800, there is a price advantage. This is to be killed.
本発明に係る製造方法によれば、このような低分子量のセルロース系繊維を用いても、十分な高強度の繊維が得ることが可能となる。 According to the production method of the present invention, it is possible to obtain sufficiently high-strength fibers even when such low molecular weight cellulose fibers are used.
（ＣＮＴ） (CNT)
本実施例のゴム構造体補強用繊維に含有されるＣＮＴとしては、平均直径（Ａｖ）と直径分布（３σ）とが０．６０>３σ／Ａｖ>０．２０という条件を満たすＣＮＴが用いられ、例えば、スーパーグロース法を用いて得られた上記条件を満たす単層ＣＮＴを用いて混練したものが挙げられる。ただし、本実施例のゴム構造体補強用繊維に含有されるＣＮＴは、上記の条件を満たすものであれば単層ＣＮＴであっても多層ＣＮＴであってもよい。また、混練に用いるＣＮＴを得るための方法についても特に限定はなく、上述のスーパーグロース法のほか、例えばｅＤＩＰＳ（改良直噴熱分解合成）法などを用いてもよい。 As the CNT contained in the fiber for reinforcing a rubber structure of this example, a CNT having an average diameter (Av) and a diameter distribution (3σ) satisfying a condition of 0.60> 3σ / Av> 0.20 is used. For example, what knead | mixed using the single-walled CNT which satisfy | fills the said conditions obtained using the super growth method is mentioned. However, the CNT contained in the fiber for reinforcing a rubber structure of the present embodiment may be a single-wall CNT or a multi-wall CNT as long as the above conditions are satisfied. Further, the method for obtaining CNTs used for kneading is not particularly limited, and for example, the eDIPS (improved direct injection pyrolysis synthesis) method may be used in addition to the above-described super-growth method.
ここでいう平均直径（Ａｖ）、直径分布（３σ）は、それぞれ透過型電子顕微鏡でＣＮＴ１００本の直径を測定した際の平均値、並びに標準偏差（σ）に３を乗じたものである。なお、本明細書における標準偏差は、標本標準偏差である。 Here, the average diameter (Av) and the diameter distribution (3σ) are obtained by multiplying the average value when the diameter of 100 CNTs is measured with a transmission electron microscope and the standard deviation (σ) by 3. In addition, the standard deviation in this specification is a sample standard deviation.
３σ／Ａｖは、ＣＮＴの直径分布を表し、この値が大きいほど直径分布が広いことを意味する。本発明において直径分布は正規分布を取るものが好ましい。ここで言う直径分布は、透過型電子顕微鏡を用いて観察できる、無作為に選択された１００本のＣＮＴの直径を測定し、その結果を用いて、横軸に直径、縦軸に頻度を取り、得られたデータをプロットし、ガウシアンで近似することで得られるものとする。異なる製法で得られたＣＮＴなどを複数種類組み合わせることでも３σ／Ａｖの値を大きくすることはできるが、その場合正規分布の直径分布を得ることは難しい。即ち、本発明においては、単独のＣＮＴ又は単独のＣＮＴに、その直径分布に影響しない量の他のＣＮＴを配合したものを用いるのが好ましい。 3σ / Av represents the CNT diameter distribution, and the larger this value, the wider the diameter distribution. In the present invention, the diameter distribution is preferably a normal distribution. The diameter distribution here refers to the measurement of the diameter of 100 randomly selected CNTs that can be observed using a transmission electron microscope, and using the results, the horizontal axis represents the diameter and the vertical axis represents the frequency. It is assumed that the obtained data is obtained by plotting and approximating with Gaussian. Although the value of 3σ / Av can be increased by combining a plurality of types of CNTs obtained by different manufacturing methods, it is difficult to obtain a normal distribution of diameter distribution. That is, in the present invention, it is preferable to use a single CNT or a single CNT blended with another CNT in an amount that does not affect the diameter distribution.
本発明においては、平均直径（Ａｖ）と直径分布（３σ）とが０．６０>３σ／Ａｖ>０．２０という条件を満たすＣＮＴを用いることにより、ＣＮＴが少量であっても、本発明が目的とするゴム構造体補強用繊維の特性である、結晶部分が多く引っ張り強度や初期引っ張り弾性率などに優れるとともに、ゴムの加硫時やゴム構造体の水分による経時劣化の少ないという特性を持つ繊維を得ることができる。なお、これらの特性をより好適に備えるゴム構造体補強用繊維を得るという観点からは、平均直径（Ａｖ）と直径分布（３σ）の条件は、０．６０>３σ／Ａｖ>０．２５であることがより好ましく、０．６０>３σ／Ａｖ>０．５０であることがさらに好ましい。 In the present invention, even when the amount of CNT is small, the present invention can be achieved by using CNT that satisfies the condition that the average diameter (Av) and the diameter distribution (3σ) are 0.60> 3σ / Av> 0.20. The properties of the target rubber structure reinforcing fiber include many crystal parts and excellent tensile strength and initial tensile elastic modulus, as well as little deterioration over time due to moisture in the rubber structure and rubber structure. Fiber can be obtained. From the viewpoint of obtaining a rubber structure reinforcing fiber having these characteristics more suitably, the average diameter (Av) and diameter distribution (3σ) conditions are 0.60> 3σ / Av> 0.25. More preferably, it is more preferably 0.60> 3σ / Av> 0.50.
０．６０>３σ／Ａｖ>０．２０という条件を満たすＣＮＴであれば特に制限なく使用することができるが、日本国特許第４６２１８９６号公報、及び日本国特許第４８１１７１２号公報に記載されているスーパーグロース法により得られるＣＮＴ（以下、「ＳＧＣＮＴ」ということがある）は、好適なＣＮＴの一例である。ＳＧＣＮＴは、ラマン分光法においてＲａｄｉａｌ Ｂｒｅａｔｈｉｎｇ Ｍｏｄｅ（ＲＢＭ）のピークを有するＣＮＴである。なお、三層以上の多層のＣＮＴのラマンスペクトルには、ＲＢＭが存在しない。スーパーグロース法を用いて得られたＣＮＴを用いた混練の手順の一例については後述する。 Any CNT satisfying the condition of 0.60> 3σ / Av> 0.20 can be used without particular limitation, but it is described in Japanese Patent No. 4621896 and Japanese Patent No. 4811712. CNT obtained by the super-growth method (hereinafter sometimes referred to as “SGCNT”) is an example of a suitable CNT. SGCNT is a CNT having a peak of Radial Breathing Mode (RBM) in Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-layer CNTs of three or more layers. An example of a kneading procedure using CNTs obtained using the super-growth method will be described later.
混練の結果得られるＣＮＴ入セルロース繊維原料におけるＣＮＴの含有量は、繊維の強度と費用を勘案して決定され得る。ＣＮＴ含有率がある程度高いほどＣＮＴ含有繊維の強度はより上がる一方、後述の実験結果に示すようにＣＮＴの含有率を低くしても十分な程度に高強度の繊維を得ることができることから、高価なＣＮＴの含有率を低く抑えることで製造コストを安価にすることが可能となる。実験の結果を踏まえた好適なＣＮＴ入繊維原料のＣＮＴの含有率は、０．００５から１．０重量％の範囲であり、さらに好適には、０．０５から０．２重量％の範囲である。これは、ＣＮＴ入繊維原料のＣＮＴの含有率０．００５重量％（さらに好適には０．０５重量％）未満であると、十分な高強度の繊維を得ることができない一方、１．０重量％（さらに好適には０．２重量％）を超えると、製造コストを安価にするというメリットが減殺されるためである。 The CNT content in the CNT-containing cellulose fiber raw material obtained as a result of kneading can be determined in consideration of the strength and cost of the fiber. The higher the CNT content, the higher the strength of the CNT-containing fibers. On the other hand, as shown in the experimental results described below, it is possible to obtain sufficiently strong fibers even if the CNT content is low. It is possible to reduce the manufacturing cost by keeping the content of CNTs low. Based on the results of the experiment, the CNT content of a suitable CNT-containing fiber raw material is in the range of 0.005 to 1.0% by weight, and more preferably in the range of 0.05 to 0.2% by weight. is there. This is because if the CNT content of the CNT-containing fiber raw material is less than 0.005% by weight (more preferably 0.05% by weight), sufficient high-strength fibers cannot be obtained, while 1.0% by weight. It is because the merit of making a manufacturing cost cheap will be reduced when it exceeds% (more preferably 0.2 weight%).
（結晶化度、結晶配向度） (Crystallinity, crystal orientation)
本実施例のゴム構造体補強用繊維は、セルロース繊維にＣＮＴを分散してその結晶性を向上させたものであり、好適には、繊維中に占める結晶部分の割合である結晶化度が６０％以上で、結晶を形成する分子が繊維軸方向に配列している程度を示す結晶配向度が０．８５以上のものである。これにより加硫処理に際してゴム構造体の力学的特性を劣化させにくいゴム構造体補強用繊維を得ることができる。この結晶化度及び結晶配向度の値については、後述の実験において確認した。当該実験は、エックス線回折による測定を行ったもので、測定には（株）リガク製ＲＵ−２００Ｂ回折計を用い、４０ｋＶ、１５０ｍＡ（波長１．５４２Å）でＣｕ−Ｋα線を照射して測定を行った。結晶化度は前散乱に対する結晶部の散乱の比率で決定した。結晶配向度は、水平方向の回折の中で最も強い反射ピークの結晶軸に対する角度から決定した。具体的な測定結果については他の測定結果とともに後述にてまとめて示す。 The fiber for reinforcing a rubber structure of this example is obtained by dispersing CNTs in cellulose fibers to improve the crystallinity, and preferably has a crystallinity of 60, which is a ratio of crystal parts in the fibers. % Or more, and the degree of crystal orientation indicating the degree to which the molecules forming the crystals are arranged in the fiber axis direction is 0.85 or more. As a result, it is possible to obtain a rubber structure reinforcing fiber that hardly deteriorates the mechanical properties of the rubber structure during the vulcanization treatment. The values of the crystallinity and crystal orientation were confirmed in the experiments described later. In this experiment, measurement was performed by X-ray diffraction. The measurement was performed by irradiating Cu-Kα rays at 40 kV, 150 mA (wavelength: 1.542 mm) using a RU-200B diffractometer manufactured by Rigaku Corporation. went. Crystallinity was determined by the ratio of crystal part scattering to pre-scattering. The degree of crystal orientation was determined from the angle of the strongest reflection peak in the horizontal diffraction with respect to the crystal axis. Specific measurement results will be described later together with other measurement results.
（引っ張り強度） (Tensile strength)
ゴム構造体補強用繊維は高強度であることが求められるところ、本実施例のゴム構造体補強用繊維の引っ張り強度の好適な値は、１ＧＰａ以上である。引っ張り強度が１ＧＰａ以上であれば、ゴム構造体補強用繊維としての使用に耐えるだけの十分な強度を保つことができる。そこで、引っ張り強度を１ＧＰａ以上とすることで、好適な高強度の繊維を得ることが可能となる。 Where the rubber structure reinforcing fiber is required to have high strength, the preferred value of the tensile strength of the rubber structure reinforcing fiber of this example is 1 GPa or more. When the tensile strength is 1 GPa or more, it is possible to maintain sufficient strength to withstand use as a rubber structure reinforcing fiber. Therefore, by setting the tensile strength to 1 GPa or more, it is possible to obtain a suitable high-strength fiber.
（初期引っ張り弾性率） (Initial tensile modulus)
また、ゴム構造体補強用繊維は高弾性率であることが求められるところ、本実施例のゴム構造体補強用繊維の初期引っ張り弾性率の好適な値は、５０ＧＰａ以上である。初期引っ張り弾性率が５０ＧＰａ以上であれば、ゴム構造体補強用繊維としての使用に耐えるだけの十分な高弾性率を保つことができる。そこで、初期引っ張り弾性率を５０ＧＰａ以上とすることで、好適な高弾性率の繊維を得ることが可能となる。 Moreover, when the rubber structure reinforcing fiber is required to have a high elastic modulus, a suitable value of the initial tensile elastic modulus of the rubber structure reinforcing fiber of this example is 50 GPa or more. If the initial tensile elastic modulus is 50 GPa or more, a sufficiently high elastic modulus sufficient to withstand use as a rubber structure reinforcing fiber can be maintained. Therefore, by setting the initial tensile elastic modulus to 50 GPa or more, it becomes possible to obtain a suitable high elastic modulus fiber.
（高温飽和水蒸気処理後の強力保持率） (Strong retention after high-temperature saturated steam treatment)
本実施例のゴム構造体補強用繊維は、高温飽和水蒸気処理（加硫処理における高温蒸着処理）後の強力保持率が９０％以上であることが望ましい。この点、従来のセルロース繊維などでは、高温飽和水蒸気処理の際、高温によるだけではなくセルロース繊維の含有水分が働きセルロースを加水分解することにより、力学特性が低下しまうという問題があった。 The reinforcing fiber for reinforcing rubber structure of this example desirably has a strength retention of 90% or more after high-temperature saturated steam treatment (high-temperature vapor deposition treatment in vulcanization treatment). In this regard, conventional cellulose fibers and the like have a problem in that the mechanical properties are deteriorated not only due to the high temperature but also due to the water content of the cellulose fibers acting and hydrolyzing the cellulose during the high temperature saturated steam treatment.
これに対し、本実施例のゴム構造体補強用繊維は、セルロースの結晶どうしを固く結束させるというＣＮＴの働きにより、結晶化度の高いものとなるため、加水分解が遅くなり、高温飽和水蒸気処理後においても高い強力保持率を得ることができる。この点についても実験で確認したところである。この実験においては、フィラメントをオートクレーブに温度１７０℃、１０分間飽和水蒸気状態で放置し、再乾燥させて強度を測定し、飽和水蒸気処理後と飽和水蒸気処理前との強度比を強度保持率として評価した。その結果については後述する。 On the other hand, the fiber for reinforcing the rubber structure of the present example has a high degree of crystallinity due to the action of CNT that tightly binds the cellulose crystals, so that the hydrolysis is slow and the high temperature saturated steam treatment Even afterwards, a high strength retention can be obtained. This point has also been confirmed by experiments. In this experiment, the filament was allowed to stand in an autoclave at a temperature of 170 ° C. for 10 minutes in a saturated water vapor state, re-dried to measure the strength, and the strength ratio after saturated steam treatment and before saturated steam treatment was evaluated as strength retention. did. The result will be described later.
<処理の流れ> <Process flow>
次に、本実施例のゴム構造体補強用繊維の製造方法にかかる処理の流れについて説明する。 Next, the flow of processing according to the method for producing a rubber structure reinforcing fiber of this example will be described.
本実施例のゴム構造体補強用繊維の製造方法は、ＣＮＴ混練ステップと、紡糸ステップとからなる。本実施例における製造方法の特徴は、このうち混練ステップに用いられるＣＮＴが、平均直径（Ａｖ）と直径分布（３σ）とが０．６０>３σ／Ａｖ>０．２０という条件を満たすＣＮＴを用いるものである点にあるものである。 The manufacturing method of the fiber for reinforcing a rubber structure according to this example includes a CNT kneading step and a spinning step. The feature of the production method in this example is that the CNT used in the kneading step is a CNT satisfying the condition that the average diameter (Av) and the diameter distribution (3σ) satisfy 0.60> 3σ / Av> 0.20. It is what is used.
以下、混練ステップにおける具体的な手順の一例について説明する。 Hereinafter, an example of a specific procedure in the kneading step will be described.
（混練ステップ） (Kneading step)
混練ステップは、ＣＮＴを繊維原料に混合し、撹拌、練合わせ等を行いつつ均一な混合状態のＣＮＴ入繊維原料を得る工程である。この工程自体は公知技術を用いて行うことが可能であり、例えば、繊維原料がセルロースの場合、混練機の中に充填したセルロース溶液中にＣＮＴを押し出し、当該溶液を撹拌し、練り合わせることなどにより行う。 The kneading step is a step of mixing the CNTs with the fiber raw material to obtain a uniform mixed CNT-containing fiber raw material while stirring, kneading and the like. This process itself can be performed using a known technique. For example, when the fiber raw material is cellulose, CNT is extruded into a cellulose solution filled in a kneader, and the solution is stirred and kneaded. To do.
混練機としては攪拌機、ホモジナイザー、超音波、ジェットミルなどが用いられるが、ＣＮＴの特性をいかすためには、ＣＮＴの機械的破壊を引き起こすおそれの少ないものが好ましい。特に上述の特許公報に記載されているスーパーグロース法により得られるＣＮＴ（ＳＧＣＮＴ）にはこうしたものが好まれる。 As the kneader, a stirrer, a homogenizer, an ultrasonic wave, a jet mill, or the like is used. In order to take advantage of the characteristics of CNT, those that are less likely to cause mechanical destruction of CNT are preferable. In particular, such a CNT (SGCNT) obtained by the super-growth method described in the above-mentioned patent publication is preferred.
分散剤としては各種界面活性剤、カルボキシメチルセルロース（ＣＭＣ）やポリビニルアルコール（ＰＶＡ）などの水溶性高分子、デオキシコール酸ナトリウム（以下ＤＯＣという）及びその誘導体などが用いられる。 Examples of the dispersant include various surfactants, water-soluble polymers such as carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA), sodium deoxycholate (hereinafter referred to as DOC), and derivatives thereof.
ここで、混練ステップにおける具体的な手順の一例として、セルロース系繊維にＣＮＴを０．１０重量％添加したセルロース再生繊維を作成する手順を以下に示す。ここでは、ＣＮＴには特許４６２１８９６号公報の記載に従ってスーパーグロース法によって得たＳＧＣＮＴを用いた。 Here, as an example of a specific procedure in the kneading step, a procedure for producing a cellulose regenerated fiber obtained by adding 0.10% by weight of CNT to a cellulosic fiber is shown below. Here, SGCNT obtained by the super-growth method according to the description of Japanese Patent No. 4621896 was used as the CNT.
具体的には次の条件において、ＣＮＴを成長させた。
炭素化合物：エチレン；供給速度５０ｓｃｃｍ
雰囲気（ガス）（Ｐａ）：ヘリウム、水素混合ガス；供給速度１０００ｓｃｃｍ
圧力１大気圧
水蒸気添加量（ｐｐｍ）：３００ｐｐｍ
反応温度（℃）：７５０℃
反応時間（分）：１０分
金属触媒（存在量）：鉄薄膜；厚さ１ｎｍ
基板：シリコンウェハー
Specifically, CNTs were grown under the following conditions.
Carbon compound: ethylene; supply rate 50 sccm
Atmosphere (gas) (Pa): Helium, hydrogen mixed gas; supply rate 1000 sccm
Pressure 1 atmospheric pressure water vapor addition amount (ppm): 300 ppm
Reaction temperature (° C): 750 ° C
Reaction time (min): 10 minutes Metal catalyst (abundance): Iron thin film; thickness 1 nm
Substrate: Silicon wafer
得られたＳＧＣＮＴでは、ＢＥＴ比表面積１，０５０ｍ２／ｇ、ラマン分光光度計での測定において、単層ＣＮＴに特長的な１００〜３００ｃｍ−１の低波数領域にラジアルブリージングモード（ＲＢＭ）のスペクトルが観察された。また、透過型電子顕微鏡を用い、無作為に１００本のＳＧＣＮＴの直径を測定した結果、平均直径（Ａｖ）が３．３ｎｍ、直径分布（３σ）が１．９、（３σ／Ａｖ）が０．５８であった。 The obtained SGCNT has a BET specific surface area of 1,050 m 2 / g and a spectrum of a radial breathing mode (RBM) in a low wavenumber region of 100 to 300 cm −1 , which is characteristic of a single-walled CNT in measurement with a Raman spectrophotometer. Was observed. In addition, as a result of measuring the diameter of 100 SGCNTs at random using a transmission electron microscope, the average diameter (Av) was 3.3 nm, the diameter distribution (3σ) was 1.9, and (3σ / Av) was 0. .58.
次いで、ＳＧＣＮＴ３．６ｍｇに、ＤＯＣ１８ｍｇと水９０ｇを加え超音波照射により分散し、さらに５重量％の完全ケン価ＰＶＡ水溶液を１０ｇ添加し超音波照射したのち、水分を除去する。次に、前記手順によって得られた該分散物にサトウキビ由来のバガスから抽出したセルロース３．６ｇを含む５重量％のＮＭＭＯ（Ｎ−メチルモルホリン−Ｎ−オキシド）一水和物を加えホモジナイザーで加熱分散し紡糸液を得た。原料セルロースの分子量は、銅／アンモニア水溶液を用いてウベローデ型粘度計により測定した結果、３８４であった。 Next, 18 mg of DOC and 90 g of water are added to 3.6 mg of SGCNT and dispersed by ultrasonic irradiation. Further, 10 g of a 5 wt% aqueous solution of a complete sapon value PVA is added and ultrasonic irradiation is performed, and then moisture is removed. Next, 5% by weight of NMMO (N-methylmorpholine-N-oxide) monohydrate containing 3.6 g of cellulose extracted from sugarcane-derived bagasse was added to the dispersion obtained by the above procedure, and heated with a homogenizer. Dispersion was obtained to obtain a spinning solution. The molecular weight of the raw material cellulose was 384 as a result of measurement with a Ubbelohde viscometer using a copper / ammonia aqueous solution.
上記と同様の方法で、パルプより得た分子量１０１０のセルロースを用い同様の紡糸液を得た。 In the same manner as described above, a similar spinning solution was obtained using cellulose having a molecular weight of 1010 obtained from pulp.
また比較例として、上記それぞれと同じセルロース（サトウキビ由来のバガスから抽出したセルロース、パルプより得た分子量１０１０のセルロース）を用い、ＣＮＴを含まない５重量％のＮＭＭＯ一水和物溶液の紡糸液を得た。 As a comparative example, the same cellulose as above (cellulose extracted from sugarcane-derived bagasse, cellulose having a molecular weight of 1010 obtained from pulp) was used, and a spinning solution of a 5 wt% NMMO monohydrate solution not containing CNTs was used. Obtained.
（紡糸ステップ） (Spinning step)
紡糸ステップは、ＣＮＴを混練したＣＮＴ入繊維原料を湿式凝固法により組織化し、巻取るステップである。ここで組織化とは、溶液中に溶かした繊維原料を凝固させ、一定程度結晶化した状態とすることをいう。 The spinning step is a step of organizing and winding up a CNT-containing fiber material kneaded with CNTs by a wet coagulation method. Here, organization means that the fiber raw material dissolved in the solution is solidified and crystallized to a certain extent.
湿式凝固法は、溶剤に溶かした繊維原料を凝固浴（水などの繊維原料を溶かさない液体浴）に吐出して固める紡糸法である。 The wet coagulation method is a spinning method in which a fiber raw material dissolved in a solvent is discharged into a coagulation bath (a liquid bath that does not dissolve fiber raw materials such as water) and hardened.
実験では、ＣＮＴを混練したＣＮＴ入繊維原料を、内径１５０μｍの吐出孔が８００個ある直径１２０ｍｍの口金のから吐出させ、５０ｍｍの空気層を通したのちＮＭＭＯ２０重量％の水溶液で凝固させ繊維束を得た。次に、該繊維束を十分水洗して乾燥させた後巻き取った。 In the experiment, a CNT-containing fiber material kneaded with CNTs was discharged from a base with a diameter of 120 mm having 800 discharge holes with an inner diameter of 150 μm, passed through a 50 mm air layer, and then solidified with an aqueous solution of 20% by weight of NMMO to form a fiber bundle. Obtained. Next, the fiber bundle was sufficiently washed with water and dried, and then wound.
表１には繊維の作成条件、繊維の性状、エックス線回折により測定した結晶配向度及び結晶化度、飽和水蒸気処理後の強度保持率を示す。 Table 1 shows fiber preparation conditions, fiber properties, crystal orientation and crystallinity measured by X-ray diffraction, and strength retention after saturated steam treatment.
（表１）
このようにして得られたゴム構造体補強用繊維は、結晶化度が６０％以上、結晶配向度が０．８５以上であり、引っ張り強度が１ＧＰａ以上であり、初期引っ張り弾性率が５０ＧＰａ以上であり、かつ乾熱収縮率が−０．２％以上であり、また、高温飽和水蒸気処理後の強力保持率が９０％以上であるという、加硫処理に際してゴム構造体の力学的特性を劣化させにくくかつ使用後の経時劣化の少ないという特性を備えたものとなる。 The rubber structure reinforcing fiber thus obtained has a crystallinity of 60% or more, a crystal orientation of 0.85 or more, a tensile strength of 1 GPa or more, and an initial tensile elastic modulus of 50 GPa or more. And the dry heat shrinkage rate is -0.2% or more, and the strength retention after high-temperature saturated steam treatment is 90% or more, which deteriorates the mechanical properties of the rubber structure during the vulcanization treatment. It is difficult and has the characteristics of little deterioration with time after use.
以上より、平均直径（Ａｖ）と直径分布（３σ）とが０．６０>３σ／Ａｖ>０．２０であるＣＮＴを用いた製造方法によって、上記のような特性を有するゴム構造体補強用繊維が得られることが確認できた。 As described above, the fiber for reinforcing a rubber structure having the above-described characteristics by a production method using CNT having an average diameter (Av) and a diameter distribution (3σ) of 0.60> 3σ / Av> 0.20. It was confirmed that
また、上記の例からは、分子量が２００以上８００以下の低分子量のセルロース繊維を用いても、十分な高強度の繊維が得られることも確認できた。 In addition, from the above examples, it was confirmed that sufficient high-strength fibers could be obtained even when low molecular weight cellulose fibers having a molecular weight of 200 or more and 800 or less were used.
なお、以上の手順においては、分散剤としてＤＯＣとＰＶＡを用いたが、本発明においては、その他の界面活性剤や水溶性高分子またはそれらの薬剤を組み合わせたものを用いてもよく、こうした分散剤を用いた場合でも、同様の特性を有するゴム構造体補強用繊維を得ることができる。 In the above procedure, DOC and PVA were used as dispersing agents. However, in the present invention, other surfactants, water-soluble polymers or combinations of these agents may be used. Even when an agent is used, a rubber structure reinforcing fiber having similar characteristics can be obtained.
<効果> <Effect>
本実施例の発明により、ＣＮＴ含有セルロース繊維からなるゴム構造体補強用繊維であって、加硫処理に際してゴム構造体の力学的特性を劣化させにくくかつ使用後の経時劣化の少ないゴム構造体補強用繊維を提供することが可能となる。また、このようなゴム構造体補強用繊維の製造方法を提供することが可能となる。 According to the invention of the present embodiment, a rubber structure reinforcing fiber made of CNT-containing cellulose fibers, which hardly deteriorates the mechanical properties of the rubber structure during vulcanization and has little deterioration over time after use. It becomes possible to provide the fiber for use. It is also possible to provide a method for producing such a rubber structure reinforcing fiber.
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