JP2006077378A - Substrate for artificial leather and method for producing the same - Google Patents
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Abstract
Description
本発明は、外観が良好で、かつ発色性、風合いおよび耐ピリング性に優れたスエード調人工皮革とすることのできる人工皮革用基材およびその製造方法に関するものである。 The present invention relates to a base material for artificial leather that can be made into a suede-like artificial leather having a good appearance and excellent color developability, texture, and pilling resistance, and a method for producing the same.
従来、繊維束と高分子弾性体とからなる基体の表面に該繊維束からなる立毛を存在させたスエード調人工皮革は公知である。そしてこのようなスエード調人工皮革の分野では、高品質化が要求され、外観（スエード感）、風合い（柔軟な手触り）、発色性（色の鮮明さ、濃度感）等の感性面での要求と、耐ピリング性等の物性面での要求をすべて高いレベルで満足するような高品質のものが求められており、これを解決すべく種々の提案がなされてきた。
例えば、外観や風合いが優れたスエード調人工皮革を得るために、人工皮革を構成している繊維を極細化する方法が一般に用いられているが、繊維を単に極細化していくと、細くなるにつれてよりくすんだ白っぽい色にしか染色できないので、外観や風合いがいくら優れていても発色性の点で劣るという欠点を有している。また、人工皮革の風合いや手触りを極めて柔軟な良好なものとするために、人工皮革を構成している繊維を極細繊維束とし、その繊維束の内部に繊維を拘束する高分子弾性体が実質的に存在させないようにすることが行われているが、繊維束の内部のみならず外周部にも実質的に繊維を拘束する高分子弾性体が存在しないので、風合いがいくら優れていても立毛面が摩擦されると立毛繊維が繊維束ごと容易に引き抜かれてしまい、いわゆる耐ピリング性の点で劣るという欠点を有している。
Conventionally, a suede-like artificial leather in which napped fibers made of a fiber bundle are present on the surface of a substrate made of a fiber bundle and a polymer elastic body is known. In the field of suede-like artificial leather, high quality is required, and there are requirements in terms of sensibility such as appearance (suede feeling), texture (soft feel), and color development (color clarity, density feeling). In addition, there is a demand for high quality products that satisfy all the requirements for physical properties such as pilling resistance at a high level, and various proposals have been made to solve this.
For example, in order to obtain a suede-like artificial leather with an excellent appearance and texture, a method of making the fibers constituting the artificial leather ultrafine is generally used, but as the fibers are simply made finer, as they become thinner Since it can only be dyed in a duller whitish color, it has the disadvantage that it is inferior in terms of color development, no matter how good the appearance and texture are. In addition, in order to make the texture and feel of artificial leather extremely soft and good, the fibers constituting the artificial leather are made into ultrafine fiber bundles, and a polymer elastic body that restrains the fibers inside the fiber bundle is substantially Although there is no polymer elastic body that substantially restrains the fiber not only in the inside of the fiber bundle but also in the outer peripheral portion, no matter how excellent the texture is, napped When the surface is rubbed, the napped fibers are easily pulled out together with the fiber bundle, which is disadvantageous in terms of so-called pilling resistance.
このようなスエード調人工皮革における立毛繊維の耐ピリング性の改良については、０．８デニール以下の極細繊維が複数本より集まった極細繊維束を発生する繊維からなるニードルパンチ不織布をポリビニルアルコール（以下、ＰＶＡと略すこともある。）水溶液へ浸漬、乾燥することで不織布形態を仮固定した後に、海島型繊維の海成分を溶解する有機溶剤中で海成分を抽出除去し、次いでポリウレタンのジメチルホルムアミド（以下、ＤＭＦと略すこともある。）溶液を含浸した後に水中で凝固してさらに表面を起毛することで得られるスエード調人工皮革において、該極細繊維中に繊維径の４分の１より大なる径を有し、かつ繊維に対して不活性な粗大粒子を添加することが提案されている（特許文献１参照）。
また、海島型繊維からなるニードルパンチ絡合不織布に、ポリウレタンのＤＭＦ溶液を含浸し水中で凝固した後に、海島型繊維の海成分を抽出除去して得られた皮革様基材を起毛して得られるスエード調人工皮革において、該基材を構成している繊維束が、０.０２〜０.２デニールの細繊維（Ａ）と、細繊維（Ａ）の平均繊度の１／５以下でかつ０.０２デニール未満の繊度の極細繊維（Ｂ）とからなり、その本数の比（Ａ／Ｂ）が２／１〜２／３であり、かつ繊維束内部には実質的に高分子弾性体が含有されておらず、さらに該立毛を構成している繊維中のＡの本数とＢの本数との比（Ａ／Ｂ）が３／１以上であることを特徴とするスエード調人工皮革が提案されている（特許文献２参照）。
また、スエ―ド調人工皮革の耐ピリング性改良については、高分子弾性体の溶剤で立毛の根元に存在する高分子弾性体の一部を溶解し、表面の立毛繊維の根元を固定する方法が提案されている（特許文献３参照）。
Regarding the improvement of the pilling resistance of napped fibers in such a suede-like artificial leather, a needle punched nonwoven fabric made of fibers that generate a bundle of ultrafine fibers in which a plurality of ultrafine fibers of 0.8 denier or less are collected is polyvinyl alcohol (hereinafter referred to as “polyvinyl alcohol”). And may be abbreviated as PVA.) After temporarily fixing the nonwoven fabric by dipping in an aqueous solution and drying, the sea component is extracted and removed in an organic solvent that dissolves the sea component of the sea-island fiber, and then polyurethane dimethylformamide (Hereinafter, it may be abbreviated as DMF.) In the suede-like artificial leather obtained by impregnating the solution and then solidifying in water and raising the surface, the ultrafine fiber has a fiber diameter larger than a quarter. It has been proposed to add coarse particles having a diameter and inert to the fibers (see Patent Document 1).
Also obtained by brushing a leather-like base material obtained by impregnating a polyurethane DMF solution into a needle punch entangled nonwoven fabric made of sea-island fibers and coagulating it in water, and then extracting and removing sea components from sea-island fibers. In the suede-like artificial leather, the fiber bundle constituting the substrate has a fine fiber (A) of 0.02 to 0.2 denier and 1/5 or less of the average fineness of the fine fiber (A) and The fine fiber (B) having a fineness of less than 0.02 denier, the ratio of the number (A / B) is 2/1 to 2/3, and the inside of the fiber bundle is substantially a polymer elastic body. Is contained, and the ratio (A / B) of the number of A to the number of B in the fibers constituting the napping is 3/1 or more, and the suede-like artificial leather is characterized in that It has been proposed (see Patent Document 2).
In addition, with regard to improving the pilling resistance of suede-like artificial leather, a method in which a part of the polymer elastic body existing at the root of the napped is dissolved with a solvent of the polymer elastic body and the root of the napped fiber on the surface is fixed. Has been proposed (see Patent Document 3).
このようなスエ―ド調人工皮革の発色性改良については、スエード調人工皮革の立毛表面に易染性樹脂を付与して染色することが提案されており（特許文献４参照）、またアルカリの存在下で還元されて水溶性となる染料で染色し、酸化して染料を固着する染色法も提案されている（特許文献５，６参照）。 For improving the color development of such a suede-like artificial leather, it has been proposed to dye a napped surface of the suede-like artificial leather with an easily dyeable resin (see Patent Document 4). There has also been proposed a dyeing method in which dyeing is performed with a dye that is reduced in the presence to become water-soluble and then oxidized to fix the dye (see Patent Documents 5 and 6).
しかしながら、特許文献１に記載の方法は、海島型繊維の海成分を抽出除去した後にポリウレタンのＤＭＦ溶液を含浸凝固する製造方法であり、極細繊維束の内部へポリウレタンが存在するため、風合いの硬化が避けられず、また、繊維中に不活性な粗大粒子が添加されていることから、柔軟な風合いや手触りを得ることができない。また、特許文献２に記載の方法は、海島型繊維の海成分を抽出除去する前にポリウレタンのＤＭＦ溶液を含浸凝固する製造方法であるため極細繊維束の外周部および内部にはポリウレタンが実質的に存在せず柔軟な風合いや手触りを得ることが可能であるが、極細繊維束にポリウレタンで固定されている部分が存在せず、耐ピリング性は不十分であった。
さらに、特許文献３に記載の方法は、皮革様基材の最表面に存在する高分子弾性体の一部を溶解して立毛繊維の根元を固定するのみで、皮革様基材の内部での繊維の固定効果に乏しく、繊維に対する高分子弾性体の把持能力が低い為、０．０１デシテックス以上の繊維に対しては、良好な耐ピリング性の改良効果が得られない。
また、上記の特許文献４、特許文献５および特許文献６に記載されているような発色性の改良方法は、発色性自体は改良できるものの、繊維立毛面の外観や触感、風合いを低下させるものであった。
However, the method described in Patent Document 1 is a production method in which a sea component of sea-island fibers is extracted and removed, and then impregnated and solidified with a DMF solution of polyurethane. Since polyurethane exists inside the ultrafine fiber bundle, the texture is cured. In addition, since inactive coarse particles are added to the fiber, it is not possible to obtain a soft texture and feel. In addition, the method described in Patent Document 2 is a manufacturing method in which a DMF solution of polyurethane is impregnated and solidified before extraction and removal of sea components of sea-island fibers, so that polyurethane is substantially not present in the outer periphery and inside of the ultrafine fiber bundle. However, there is no portion fixed to the ultrafine fiber bundle with polyurethane, and the pilling resistance is insufficient.
Furthermore, the method described in Patent Document 3 only dissolves a part of the polymer elastic body existing on the outermost surface of the leather-like base material and fixes the roots of the napped fibers, and the inside of the leather-like base material. Since the fiber fixing effect is poor and the gripping ability of the polymer elastic body to the fiber is low, a good pilling resistance improving effect cannot be obtained for fibers of 0.01 dtex or more.
Moreover, although the coloring property improving method as described in Patent Document 4, Patent Document 5, and Patent Document 6 described above can improve the coloring property itself, it reduces the appearance, feel and texture of the fiber raised surface. Met.
本発明は、風合い、外観が良好で、かつ発色性と耐ピリング性に優れており、衣料用、靴用、袋物用、家具用、カーシート用、ゴルフ手袋等の各種スポーツ手袋用に好適に使用できるスエード調人工皮革とすることのできる人工皮革用基材およびその製造方法を提供することを目的とする。 The present invention has a good texture and appearance, is excellent in color development and pilling resistance, and is suitable for various sports gloves such as clothing, shoes, bags, furniture, car seats, and golf gloves. An object of the present invention is to provide a base material for artificial leather that can be used as a suede-like artificial leather and a method for producing the same.
発明者らは、前記の目的を達成するために鋭意研究を行った結果、高分子弾性体に接触した極細繊維束の最外周に配置された極細繊維は高分子弾性体に接着しているが、極細繊維束の内部および高分子弾性体に接触していない極細繊維束の最外周の極細繊維は高分子弾性体に接着していない構造を実現することで、風合い、外観が良好で、かつ発色性と耐ピリング性に優れた、衣料用、靴用、袋物用、家具用、カーシート用、ゴルフ手袋等の各種スポーツ手袋用に好適に使用できるスエード調人工皮革、およびその製造方法を提供できることを見出し、本発明を完成したものである。
すなわち、本発明は、
（１）０．０１デシテックスから０．３デシテックスの極細繊維が１０本から２５０本集束した極細繊維束からなる絡合不織布に高分子弾性体が含有された人工皮革用基材内部の高分子弾性体と極細繊維束の少なくとも一部分以上が接着している状態において、接着している極細繊維束の最外周に配置された極細繊維は高分子弾性体と接着しているが、最外周以外の極細繊維は高分子弾性体と接着していないことを特徴とする人工皮革用基材である。
また、（２）０．０１デシテックスから０．３デシテックスの極細繊維が１０本から２５０本集束した極細繊維束からなる絡合不織布に高分子弾性体が含有された人工皮革用基材を製造するに際し、
（Ｉ）海島型繊維の横断面において、海島型繊維の外周に配置された島成分の外周長の５％から３０％が、海島型繊維の外周表面に露出している海島型繊維からなる絡合不織布を製造する工程、
（ＩＩ）該絡合不織布の内部に高分子弾性体を付与する工程、
（ＩＩＩ）海島型繊維を極細繊維束に変性する工程
を順次行うことを特徴とする人工皮革用基材の製造方法である。
そして、（３）（１）記載の人工皮革用基材の少なくとも片面に極細繊維からなる立毛が形成されたスエード調人工皮革である。
As a result of intensive studies to achieve the above object, the inventors have found that the ultrafine fibers arranged on the outermost periphery of the ultrafine fiber bundle in contact with the polymer elastic body are bonded to the polymer elastic body. By realizing a structure in which the ultrafine fibers in the ultrafine fiber bundle and the outermost circumference of the ultrafine fiber bundle not in contact with the polymer elastic body are not bonded to the polymer elastic body, the texture and appearance are good, and Provided suede-like artificial leather with excellent color development and pilling resistance, suitable for various sports gloves such as clothing, shoes, bags, furniture, car seats, and golf gloves, and its manufacturing method The present invention has been found out and the present invention has been completed.
That is, the present invention
(1) Polymer elasticity inside a base material for artificial leather, in which a polymer elastic body is contained in an entangled nonwoven fabric made of a bundle of ultrafine fibers in which 10 to 250 ultrafine fibers of 0.01 to 0.3 decitex are converged In the state where at least a part of the ultrafine fiber bundle is bonded to the body, the ultrafine fibers arranged on the outermost periphery of the bonded ultrafine fiber bundle are bonded to the polymer elastic body. The fiber is a base material for artificial leather, characterized in that the fiber is not bonded to the polymer elastic body.
(2) Producing a base material for artificial leather, in which a polymer elastic body is contained in an entangled nonwoven fabric composed of a bundle of ultrafine fibers in which 10 to 250 ultrafine fibers of 0.01 to 0.3 decitex are converged On the occasion
(I) In the cross section of the sea-island type fiber, a tangle of sea-island type fibers in which 5% to 30% of the outer circumference length of the island component arranged on the outer circumference of the sea-island type fiber is exposed on the outer circumferential surface of the sea-island type fiber A process for producing a synthetic nonwoven fabric,
(II) providing a polymer elastic body in the entangled nonwoven fabric;
(III) A method for producing a base material for artificial leather, comprising sequentially performing a step of modifying sea-island type fibers into ultrafine fiber bundles.
(3) A suede-like artificial leather in which napped fibers made of ultrafine fibers are formed on at least one surface of the base material for artificial leather described in (1).
本発明の人工皮革用基材は、風合い、外観が良好で、かつ発色性と耐ピリング性に優れたスエード調人工皮革用の人工皮革用基材である。 The base material for artificial leather of the present invention is a base material for artificial leather for suede-like artificial leather having a good texture and appearance, and excellent color development and pilling resistance.
本発明の人工皮革用基材は、例えば、以下の工程（ａ）〜（ｄ）、
（ａ）海島型繊維であって、該海島型横断面の外周に配置された島成分の外周長の５％から３０％が、海島型繊維の外周表面に露出し、単繊維繊度０．０１デシテックスから０．３デシテックスの極細繊維が１０本から２５０本集束した極細繊維束を発生させ得る海島型繊維を製造する工程、
（ｂ）該海島型繊維からなるウェブをニードルパンチ法により三次元絡合させ絡合不織布を製造する工程、
（ｃ）該絡合不織布に高分子弾性体溶液を含浸し、湿式凝固する工程、
（ｄ）海成分を除去することにより該繊維を極細繊維からなる繊維束に変成する工程、
を順次行なうことにより得ることができる。
また、得られた人工皮革用基材について以下の工程（ｅ）（ｆ）、
（ｅ）少なくとも一面に立毛を形成させる工程、
（ｆ）必要に応じて（ｅ）の前または後で染色、あるいは整毛する工程、
を行なうことにより、本発明の効果を有するスエード調人工皮革を得ることができる。
The base material for artificial leather of the present invention includes, for example, the following steps (a) to (d),
(A) 5 to 30% of the outer periphery length of the island component arranged on the outer periphery of the sea-island type cross section is exposed on the outer peripheral surface of the sea-island type fiber, and the single fiber fineness is 0.01 Manufacturing a sea-island type fiber capable of generating a bundle of ultrafine fibers in which 10 to 250 ultrafine fibers of 0.3 decitex are converged from decitex;
(B) a step of producing an entangled nonwoven fabric by three-dimensionally intertwining the web made of the sea-island fibers by a needle punch method;
(C) impregnating the entangled nonwoven fabric with a polymer elastic body solution and wet coagulating it;
(D) a step of transforming the fiber into a fiber bundle composed of ultrafine fibers by removing sea components;
Can be obtained sequentially.
Moreover, the following steps (e) and (f) for the obtained base material for artificial leather,
(E) forming napped hairs on at least one surface;
(F) a step of dyeing or hair shaping before or after (e) as necessary;
By performing the above, a suede-like artificial leather having the effects of the present invention can be obtained.
本発明の海島型繊維において、島成分を構成するポリマーは、例えば、ナイロン６、ナイロン６６をはじめとする溶融紡糸可能なポリアミド類、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、カチオン可染型変性ポリエチレンテレフタレートをはじめとする溶融紡糸可能なポリエステル類などから選ばれた少なくとも１種類のポリマーである。 In the sea-island fiber of the present invention, the polymer constituting the island component is, for example, polyamides such as nylon 6 and nylon 66 that can be melt-spun, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and cationic dyeable type. It is at least one polymer selected from melt-spun polyesters including modified polyethylene terephthalate.
一方、海成分を構成するポリマーは、島成分を構成するポリマーとは溶剤または分解剤に対する溶解性または分解性を異にし、即ち海成分を構成するポリマーの方が島成分を構成するポリマーよりは特定の溶剤または分解剤に対する溶解性または分解性が大きく、島成分を構成するポリマーとの親和性が小さいポリマーであって、かつ紡糸条件下で島成分の溶融粘度より小さい溶融粘度であるか、あるいは表面張力の小さいポリマーであり、例えば、ポリエチレン、ポリスチレン、変性ポリスチレン、エチレンプロピレン共重合体などの易溶解性のポリマーや、スルホイソフタル酸ナトリウムやポリエチレングリコール等で変性したポリエチレンテレフタレートなどの易分解性のポリマーから選ばれた少なくとも１種類のポリマーである。 On the other hand, the polymer constituting the sea component differs from the polymer constituting the island component in solubility or decomposability with respect to the solvent or the decomposing agent, that is, the polymer constituting the sea component is more than the polymer constituting the island component. A polymer having high solubility or decomposability with respect to a specific solvent or decomposing agent and low affinity with a polymer constituting the island component, and having a melt viscosity smaller than the melt viscosity of the island component under the spinning conditions, Alternatively, it is a polymer with a low surface tension, for example, a readily soluble polymer such as polyethylene, polystyrene, modified polystyrene, and ethylene propylene copolymer, or a readily degradable polymer such as polyethylene terephthalate modified with sodium sulfoisophthalate or polyethylene glycol. And at least one polymer selected from the polymers.
図１は、本発明の海島型繊維の１態様を示す断面模式図である。図に示されているように、海島型繊維は、溶解または分解除去することのできる海成分ポリマー中に、０．０１デシテックスから０．３デシテックスの極細繊維となる島成分が１０から２５０分散配置されている海島型繊維であって、海島型繊維断面において外周部に配置された島成分の外周長の５％から３０％が海島型繊維の表面に露出している海島型繊維である。ここで、海島型繊維の表面に露出した島成分の外周長の割合は図２に示す通り、海島型繊維の横断面において、外周に配置された島成分の外周長（Ｘ）と島成分の外周において、海島型繊維の海成分より露出した部分の周長（Ｙ）を測定し、任意の２０本の海島型繊維において算出した（Ｙ）／（Ｘ）の平均値より求めた割合をいう。繊維表面への島成分の露出割合が５％未満だと、得られる人工皮革用基材において極細繊維束を包囲する高分子弾性体と外周の極細繊維との接着力が不足してしまうので、耐ピリング性において本発明が目的とするレベルは得られず、逆に、３０％より大きくなると外周部に配置されて高分子弾性体に接着する極細繊維の接着力が強くなり過ぎるので風合いなどにおいて本発明が目的とするレベルが得られなくなる。
このような海島型繊維は、海成分ポリマーと島成分ポリマーとを別の系で溶融し、紡糸頭部で接合−分割を複数回繰り返して両者の混合系を形成して紡糸する方法、あるいは両者を紡糸口金部で繊維形状を規定して合流させ紡糸する方法等により得られる。ここで、より安定して島成分が１０本から２５０本集束した海島型繊維であって、その横断面における外周に配置された島成分の外周長の５％から３０％が、海島型繊維の外周表面に露出している海島型繊維を得るための手段としては、海島型繊維の海成分比率を低下させる方法、ノズルパック内の紡糸口金部分の海成分と島成分が接合してから吐出される部分で海成分の圧力上昇を抑制し、かつ島成分の圧力を上昇させる方法、海島型繊維の外周に配置された島成分が、海島型繊維の外周に露出するように流路を規制する方法等があるが、これらの方法に限定される物ではない。
FIG. 1 is a schematic cross-sectional view showing one embodiment of the sea-island fiber of the present invention. As shown in the figure, in the sea-island type fiber, 10 to 250 dispersed island components that form 0.01 decitex to 0.3 decitex ultrafine fibers are dispersed in a sea component polymer that can be dissolved or decomposed and removed. The sea-island type fiber is a sea-island type fiber in which 5% to 30% of the outer peripheral length of the island component arranged on the outer peripheral portion in the cross-section of the sea-island type fiber is exposed on the surface of the sea-island type fiber. Here, the ratio of the outer peripheral length of the island component exposed on the surface of the sea-island fiber is as shown in FIG. 2, in the cross section of the sea-island fiber, the outer peripheral length (X) of the island component arranged on the outer periphery and the island component In the outer periphery, the circumference (Y) of the portion exposed from the sea component of the sea-island fiber is measured, and the ratio obtained from the average value of (Y) / (X) calculated for any 20 sea-island fibers is said. . When the exposure ratio of the island component to the fiber surface is less than 5%, the adhesive force between the polymer elastic body surrounding the ultrafine fiber bundle and the ultrafine fiber on the outer periphery is insufficient in the obtained base material for artificial leather. In the pilling resistance, the target level of the present invention cannot be obtained. Conversely, when it exceeds 30%, the adhesion force of the ultrafine fibers disposed on the outer peripheral portion and bonded to the polymer elastic body becomes too strong. The target level of the present invention cannot be obtained.
Such a sea-island type fiber is a method in which a sea component polymer and an island component polymer are melted in different systems, and the spun head is repeatedly spliced and divided multiple times to form a mixed system of the two, or both. Are obtained by, for example, a method in which the fiber shape is defined at the spinneret portion to join and spin. Here, sea island type fibers in which 10 to 250 island components are more stably focused, and 5% to 30% of the outer circumference length of the island components arranged on the outer circumference in the cross section thereof are the sea island type fibers. As a means for obtaining sea-island type fibers exposed on the outer peripheral surface, a method of reducing the sea component ratio of sea-island type fibers, the sea component and the island component of the spinneret portion in the nozzle pack are joined and discharged. To suppress the rise in the pressure of the sea component and increase the pressure of the island component, and to regulate the flow path so that the island component arranged on the outer periphery of the sea-island fiber is exposed on the outer periphery of the sea-island fiber There are methods, but the method is not limited to these methods.
ここで、海島型繊維を構成する島成分の本数は１０本から２５０本であることが重要で、好ましくは１５本から１００本である。島成分の本数が１０本未満の場合は、最外周に配置されて高分子弾性体に接着し得る極細繊維の繊維全体に占める割合が高すぎ、実質的な極細繊維の拘束状態が過剰となるため、本発明が目的とするような良好な風合いの人工皮革用基材は得られない。一方、島成分の本数が２５０本を超える場合は、高分子弾性体と接着し得る極細繊維の繊維全体に占める割合が小さすぎ、実質的な極細繊維の拘束状態が過小となるため、風合いは十分以上に良好なものは得られるが、本発明が目的とするような耐ピリング性の良好な人工皮革用基材を得ることが出来なくなる。 Here, it is important that the number of island components constituting the sea-island fiber is 10 to 250, and preferably 15 to 100. When the number of island components is less than 10, the proportion of the ultrafine fibers that can be adhered to the polymer elastic body and disposed on the outermost periphery is too high, and the restraint state of the substantial ultrafine fibers becomes excessive. Therefore, an artificial leather base material having a good texture as intended by the present invention cannot be obtained. On the other hand, if the number of island components exceeds 250, the ratio of the ultrafine fibers that can be bonded to the polymer elastic body to the whole fiber is too small, and the restraint state of the substantial ultrafine fibers is too small, so the texture is Although it is possible to obtain a material that is better than sufficient, it becomes impossible to obtain a base material for artificial leather having good pilling resistance as intended by the present invention.
また、極細繊維の繊度は、耐ピリング性と発色性との関係から０．０１デシテックスから０．３デシテックスの範囲であることが必須である。極細繊維の繊度が０．０１デシテックスに満たない場合は、くすんだ白っぽい色にしか染色できず、鮮やかな色を有するものが得られず、発色性の点で劣るという欠点を有している。また、０．３デシテックスを超える場合は、染色後の色の鮮明さや発色性は良好となるが、繊維強度が増加して耐ピリング性を良好に保つためには、高分子弾性体比率を増加する必要があり、結果として風合いおよびタッチの硬化が起こり、良好なスエード調人工皮革が得られない。 In addition, the fineness of the ultrafine fiber is essential to be in the range of 0.01 dtex to 0.3 dtex from the relationship between pilling resistance and color development. When the fineness of the ultrafine fiber is less than 0.01 dtex, it can be dyed only in a dull whitish color, and a product having a vivid color cannot be obtained, resulting in inferior color development. Also, if it exceeds 0.3 decitex, the color clarity and color developability after dyeing will be good, but in order to maintain good pilling resistance by increasing fiber strength, the ratio of polymer elastic body is increased. As a result, texture and touch hardening occur, and a good suede-like artificial leather cannot be obtained.
海島型繊維は、必要に応じて延伸、捲縮、熱固定、カットなどの処理工程を経て繊度２〜１０デシテックスのステープルあるいはフィラメントとする。なお、本発明で言う繊度及び平均繊度は海島型繊維の断面から容易に求められる、すなわち海島型繊維の断面の顕微鏡写真を撮り、島成分（極細繊維）の本数を数え、長さ１００００ｍの繊維を構成している海島型繊維の質量と島成分の比率から島成分の質量を算出し、島成分の本数で割ることで島成分の繊度を求めることが出来る。海島型繊維を極細繊維の繊維束に変成したのちの繊維束については、顕微鏡写真で極細繊維の直径を測定して、島成分を構成するポリマーの比重から長さ１００００ｍの重量を計算することにより極細繊維の繊度が求められる。 The sea-island type fibers are made into staples or filaments having a fineness of 2 to 10 dtex through processing steps such as drawing, crimping, heat setting, and cutting as necessary. The fineness and average fineness referred to in the present invention can be easily determined from the cross section of the sea-island fiber, that is, a micrograph of the cross-section of the sea-island fiber is taken, the number of island components (ultrafine fibers) is counted, and the fiber having a length of 10,000 m The mass of the island component is calculated from the ratio of the sea-island fiber constituting the island and the ratio of the island component, and the fineness of the island component can be obtained by dividing by the number of island components. For the fiber bundle after the sea-island type fiber is transformed into a fiber bundle of ultrafine fibers, the diameter of the ultrafine fiber is measured with a micrograph, and the weight of 10,000 m in length is calculated from the specific gravity of the polymer constituting the island component. The fineness of ultrafine fibers is required.
海島型繊維がステープルの場合、該ステープルをカードで解繊し、ウェバーを通してランダムウェブまたはクロスラップウェブを形成し、得られた繊維ウェブを所望の重さ、厚さに積層する。次いで、ニードルパンチ、高速流体流などの公知の方法で絡合処理を行なって絡合不織布とする。絡合不織布化する際に、本発明の効果を損なわない範囲で、上記海島型繊維以外の繊維を少量添加してもよい。 When the sea-island fiber is a staple, the staple is defibrated with a card, a random web or a cross-wrap web is formed through a webber, and the obtained fiber web is laminated to a desired weight and thickness. Next, an entangled nonwoven fabric is obtained by performing an entanglement process by a known method such as needle punching or high-speed fluid flow. When forming an entangled nonwoven fabric, a small amount of fibers other than the sea-island type fibers may be added as long as the effects of the present invention are not impaired.
次に絡合不織布に高分子弾性体を含浸し、凝固する。絡合不織布に含浸する高分子弾性体は、人工皮革用基材に用いられる公知のものが用いられる。例えば、ポリエステルジオール、ポリエーテルジオール、ポリエーテルエステルジオール、ポリカーボネートジオールなどから選ばれた少なくとも１種類の平均分子量５００〜３０００のポリマージオールと、４，４’−ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネートなどの、芳香族系、脂環族系、脂肪族系のジイソシアネートなどから選ばれた少なくとも１種のジイソシアネートと、エチレングリコール、エチレンジアミン等の２個以上の活性水素原子を有する少なくとも１種の低分子化合物とを所定のモル比で反応させて得たポリウレタンであることが得られる人工皮革の風合や力学的物性に優れる点で好ましい。ポリウレタンは、必要に応じて、合成ゴム、ポリエステルエラストマーなどの高分子弾性体を添加した高分子弾性体組成物として使用することもできる。 Next, the entangled nonwoven fabric is impregnated with a polymer elastic body and solidified. As the polymer elastic body impregnated into the entangled nonwoven fabric, known materials used for base materials for artificial leather are used. For example, at least one polymer diol having an average molecular weight of 500 to 3000 selected from polyester diol, polyether diol, polyether ester diol, polycarbonate diol, etc., 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. At least one diisocyanate selected from aromatic, alicyclic and aliphatic diisocyanates and at least one low molecular weight compound having two or more active hydrogen atoms such as ethylene glycol and ethylenediamine It is preferable in that it is a polyurethane obtained by reacting and at a predetermined molar ratio in that the artificial leather obtained has excellent texture and mechanical properties. Polyurethane can also be used as a polymer elastic body composition to which a polymer elastic body such as synthetic rubber or polyester elastomer is added, if necessary.
ポリウレタンを主体とした高分子弾性体組成物などの高分子弾性体を溶剤に溶解あるいは分散剤に分散させて高分子弾性体液としたのち、これを絡合不織布に含浸し、高分子弾性体の非溶剤で処理して湿式凝固するか、あるいは感熱ゲル化処理して乾式凝固して繊維質基体とする。高分子弾性体液には必要に応じて着色剤、凝固調節剤、酸化防止剤等の如き添加剤を配合することもできる。繊維質基体に占める高分子弾性体あるいは高分子弾性体組成物の量は、目的とする用途に応じて風合いを調整するために、増減可能であるが、固形分として質量比で１０〜５０％の範囲が好ましい。固形分で１０％に満たない場合は、最終製品である人工皮革用基材あるいはスエード調人工皮革において、極細繊維束に接触して最外周の極細繊維に接着するための高分子弾性体が不十分なため良好な耐ピリング性を得ることが出来ない。また、５０％を超える場合には、耐ピリング性への悪影響は生じず、むしろ向上する傾向にあるが、その一方で人工皮革用基材あるいはスエード調人工皮革の手触りや風合いが硬化し、ゴム感が増大するので好ましくなく、これを抑えるための対策は、通常であれば高分子弾性体を含浸、凝固する前の絡合不織布へＰＶＡ等の溶解除去可能な樹脂を高分子弾性体の付与量に応じて多量に付与して繊維と高分子弾性体との間に介在させ、繊維を極細繊維化した後で、あるいは同時にこれを除去するなどの工程を追加する方法が挙げられるが、本発明において極細繊維束に接触して最外周の極細繊維に高分子弾性体を接着させるのには不向きな対策であり好ましくない。但し、例えば絡合不織布の形態を仮固定して、工程通過性を確保するなどのために、前記のように本発明の目的が阻害されるようなことがない範囲で、少量のＰＶＡ等の溶解除去可能な樹脂を付与してもよい。また、高分子弾性体と極細繊維束の最外周に存在する極細繊維の接着状態は、図３に示す様に極細繊維束を高分子弾性体が完全に包み込んで、極細繊維束の最外周の極細繊維と接着し、極細繊維束の最外周以外の極細繊維は接着せずに取り囲んでいる状態、図４に示す様に高分子弾性体が極細繊維束を部分的に包み込んで、極細繊維束の最外周の一部の極細繊維と接着し、極細繊維束の最外周の他の部分と最外周以外の極細繊維は接着せずに取り囲んでいる状態、図５に示す様に高分子弾性体が極細繊維束の最外周の極細繊維に複数箇所接着しておりそれ以外の最外周の極細繊維と最外周以外の極細繊維は接着していない状態、または、それぞれが混在するのが一般的であり、人工皮革用基材における絡合不織布に占める高分子弾性体あるいは高分子弾性体組成物の量が多くなると図３の状態が多く観察され、人工皮革用基材における絡合不織布に占める高分子弾性体の量が少なくなると図５の状態が多く観察される。本発明において、高分子弾性体と極細繊維束の存在する部分においては、高分子弾性体と極細繊維束の最外周に存在する極細繊維の接着が認められ、高分子弾性体の存在する部分において効率的に極細繊維束の最外周に存在する極細繊維と接着することにより高い耐ピリング性とソフト性を両立して発揮することが出来る。 A polymer elastic body such as a polymer elastic body composition mainly composed of polyurethane is dissolved in a solvent or dispersed in a dispersant to obtain a polymer elastic body liquid, which is then impregnated into an entangled nonwoven fabric, It is treated with a non-solvent and wet-solidified, or heat-sensitive gelled and dry-solidified to obtain a fibrous substrate. Additives such as a colorant, a coagulation regulator, and an antioxidant can be added to the polymer elastic body fluid as necessary. The amount of the polymer elastic body or the polymer elastic body composition in the fibrous substrate can be increased or decreased in order to adjust the texture according to the intended use, but it is 10 to 50% in terms of mass ratio as a solid content. The range of is preferable. When the solid content is less than 10%, there is no polymer elastic body for contacting the ultrafine fiber bundle and adhering to the outermost ultrafine fiber in the artificial leather base material or suede-like artificial leather as the final product. Since it is sufficient, good pilling resistance cannot be obtained. On the other hand, when it exceeds 50%, there is no adverse effect on the pilling resistance, and it tends to be improved. It is not preferable because the feeling increases, and measures to suppress this are usually applied by applying a polymer elastic body to a entangled nonwoven fabric before impregnating and solidifying the polymer elastic body, such as PVA. A method of adding a large amount according to the amount and interposing between the fiber and the polymer elastic body and adding a step such as removing the fiber after forming the fiber into ultrafine fibers or at the same time can be mentioned. In the present invention, it is unsuitable measure to contact the ultrafine fiber bundle and adhere the polymer elastic body to the outermost ultrafine fiber, which is not preferable. However, for example, in order to temporarily fix the form of the entangled nonwoven fabric and to ensure process passability, the amount of PVA or the like is small so long as the object of the present invention is not hindered. A resin that can be dissolved and removed may be added. Further, the adhesion state of the ultrafine fiber existing on the outermost periphery of the polymer elastic body and the ultrafine fiber bundle is such that the ultrafine fiber bundle is completely wrapped by the polymer elastic body as shown in FIG. The ultrafine fiber bundle is partially wrapped around the ultrafine fiber bundle as shown in FIG. The polymer elastic body as shown in FIG. 5, in a state in which it is bonded to a part of the ultrafine fiber on the outermost periphery of the fiber and the other part of the outermost periphery of the ultrafine fiber bundle is surrounded without being bonded. Is bonded to the outermost ultrafine fiber of the ultrafine fiber bundle and other outermost ultrafine fibers and non-outermost ultrafine fibers are not bonded, or they are generally mixed. Yes, a polymer elastic body in the entangled nonwoven fabric in the base material for artificial leather Is the amount is increased when the observation that many state of FIG. 3 of the elastic polymer composition, the state of FIG. 5 is often observed when the amount of the elastic polymer occupying the entangled nonwoven fabric in the artificial leather base material is reduced. In the present invention, in the portion where the polymer elastic body and the ultrafine fiber bundle are present, adhesion between the polymer elastic body and the ultrafine fiber existing on the outermost periphery of the ultrafine fiber bundle is recognized, and in the portion where the polymer elastic body exists. High pilling resistance and softness can be exhibited at the same time by efficiently bonding to the ultrafine fibers present on the outermost periphery of the ultrafine fiber bundle.
高分子弾性体を含浸して凝固させた繊維質基体を、極細繊維成分および高分子弾性体の非溶剤であり、かつ海島型繊維の海成分の溶剤または分解剤である液体で処理して、海島型繊維から極細繊維を発生させる。例えば高分子弾性体がポリウレタンのとき、島成分がナイロンやポリエチレンテレフタレートであり、海成分がポリエチレンである場合には、溶剤としてトルエン、トリクロロエチレン、テトラクロロエチレンなどが使用され、また極細繊維成分がナイロンやポリエチレンテレフタレートであり、海成分が易アルカリ分解性の変性ポリエステルである場合には、分解剤として苛性ソーダ水溶液などが使用される。このような処理により、海島型繊維から海成分が除去されて、海島型繊維は極細繊維束に変成され、本発明の人工皮革用基材が得られる。
このようにして得られた人工皮革用基材を構成する極細繊維束の最外周に配置された極細繊維は、変成前の段階で海島型繊維の断面における外周、即ち繊維表面と高分子弾性体とが接着している場合には、変成後でも高分子弾性体との接着状態が実質的に大半が維持されており、これによって外的摩擦力等による極細繊維束自体の抜けが抑制され、また高分子弾性体が極細繊維束のバインダーとしての役割を少量でも効果的に発揮するので、人工皮革用基材あるいは人工皮革用基材を起毛して得たスエード調人工皮革としての手触りや風合いにおいて過剰な硬化を引き起こすような過剰量の高分子弾性体を人工皮革表面等に付与することなく、耐ピリング性に効果を発揮する。また、含浸した高分子弾性体を固化させた後で海島型繊維を極細繊維束に変成させるため、変成後の極細繊維束の内部には高分子弾性体は実質的に存在しないので、極細繊維束の最外周部が高分子弾性体に接着しており見掛け上は極細繊維束が拘束されているように見えても、実際には人工皮革用基材、あるいはスエード調人工皮革としたときの手触りや風合いの過剰な硬化が引き起こされるものではない。
A fibrous base material impregnated and solidified with a polymer elastic body is treated with a liquid that is a non-solvent for the ultrafine fiber component and the polymer elastic body, and a sea component solvent or decomposition agent for the sea-island fiber, Superfine fibers are generated from sea-island type fibers. For example, when the elastic polymer is polyurethane, when the island component is nylon or polyethylene terephthalate and the sea component is polyethylene, toluene, trichlorethylene, tetrachloroethylene, etc. are used as the solvent, and the ultrafine fiber component is nylon or polyethylene. When it is terephthalate and the sea component is an easily alkali-decomposable modified polyester, an aqueous caustic soda solution or the like is used as a decomposing agent. By such treatment, sea components are removed from the sea-island type fibers, and the sea-island type fibers are transformed into ultrafine fiber bundles, thereby obtaining the artificial leather substrate of the present invention.
The ultrafine fibers arranged on the outermost periphery of the ultrafine fiber bundle constituting the artificial leather substrate thus obtained are the outer periphery in the cross section of the sea-island type fiber before the transformation, that is, the fiber surface and the polymer elastic body. Are attached to the polymer elastic body even after the transformation, and most of the adhesion state with the polymer elastic body is maintained, thereby suppressing the removal of the ultrafine fiber bundle itself due to external frictional force, In addition, since the polymer elastic body effectively plays a role as a binder for ultrafine fiber bundles even in a small amount, the feel and texture as a suede-like artificial leather obtained by raising a base material for artificial leather or a base material for artificial leather It exerts an effect on pilling resistance without imparting an excessive amount of a polymer elastic body that causes excessive curing in the artificial leather surface or the like. Also, since the sea-island type fibers are transformed into ultrafine fiber bundles after the impregnated polymer elastic bodies are solidified, there is substantially no polymer elastic body inside the ultrafine fiber bundles after the transformation. Even though the outermost periphery of the bundle is bonded to the polymer elastic body and the ultrafine fiber bundle appears to be constrained, it is actually a base material for artificial leather or suede-like artificial leather. It does not cause excessive hardening of the touch or texture.
次に、この人工皮革用基材を必要により厚さ方向に複数枚にスライスし、あるいは裏面となる一面を研削するなどして厚さを調節した後、少なくとも表面となる一面を起毛処理して極細繊維を主体とした繊維立毛面を形成させ、スエード調人工皮革とする。繊維立毛面を形成させる方法は、サンドペーパーや針布などによるバフィング等の公知の方法を用いることができる。起毛処理の前あるいは後に、高分子弾性体を溶解または膨潤させることのできる溶剤、即ち高分子弾性体がポリウレタンであればジメチルホルムアミド（ＤＭＦ）などを含む処理液を起毛処理する表面に塗布して、高分子弾性体の接着による極細繊維束の拘束状態を微調整することも、本発明の効果を阻害しない範囲で必要に応じて追加することができる。 Next, after slicing the base material for artificial leather into a plurality of sheets in the thickness direction as necessary, or adjusting the thickness by grinding one surface that is the back surface, at least one surface that is the surface is brushed A fiber raised surface mainly composed of ultrafine fibers is formed to form a suede-like artificial leather. As a method for forming the fiber raised surface, a known method such as buffing with sandpaper or a needle cloth can be used. Before or after the raising treatment, a solvent capable of dissolving or swelling the polymer elastic body, that is, a treatment liquid containing dimethylformamide (DMF) or the like is applied to the surface to be raised if the polymer elastic body is polyurethane. Fine adjustment of the restraint state of the ultrafine fiber bundle by adhesion of the polymer elastic body can also be added as necessary within the range not impairing the effect of the present invention.
得られたスエード調人工皮革は、必要に応じて染色することができ、採用できる染色方法は、繊維の種類に応じて適宜選択される酸性染料、金属錯塩染料、分散染料などを主体とした染料を用いて、通常使用されるようなパッダー、ジッガー、サーキュラー、ウィンスなどの公知の染色機を使用した、従来公知の染色方法である。また、スエード調人工皮革は、染色以外にも必要に応じて、機械もみ処理、柔軟剤処理、ブラッシング、防燃剤等の機能性添加剤付与処理、着色剤や樹脂などを塗布するなどによる意匠性付与処理などの仕上げ処理を行なうこともできる。 The obtained suede-like artificial leather can be dyed as necessary, and the dyeing method that can be adopted is a dye mainly composed of an acid dye, a metal complex dye, a disperse dye, etc., which are appropriately selected according to the type of fiber. Is a conventionally known dyeing method using a known dyeing machine such as a padder, jigger, circular, and wince. In addition to dyeing, suede-like artificial leather can be designed by applying mechanical additives such as mechanical fouling, softener treatment, brushing, and flame retardants, and by applying colorants and resins. A finishing process such as an applying process can also be performed.
本発明で得られたスエード調人工皮革は、外観、風合いが良好で、かつ発色性、耐ピリング性に優れたものである。 The suede-like artificial leather obtained in the present invention has a good appearance and texture, and is excellent in color development and pilling resistance.
次に、本発明の実施態様を具体的な実施例で説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例中の部および％は、ことわりのない限り質量に関するものである。
＜繊度測定方法＞
人工皮革用基材の繊維束の断面を電子顕微鏡で２０００倍に拡大して写真に撮り極細繊維の直径を任意３箇所の極細繊維束について測定して、島成分を構成するポリマーの比重から長さ１００００ｍの重量を計算することにより極細繊維の繊度および平均繊度を算出した。
＜島成分の露出割合の測定方法＞
紡糸時に採取した放流糸の断面を電子顕微鏡で１０００倍に拡大して写真に撮り、図２に示す通り、海島型繊維の横断面において、外周に配置された個々の島成分の外周長（Ｘ）と、該島成分の外周において海島型繊維の海成分より露出した部分の周長（Ｙ）をそれぞれ測定し、（Ｙ）／（Ｘ）の平均値を算出し、さらに任意の２０本の海島型繊維において算出した（Ｙ）／（Ｘ）の平均値より求めた。
＜風合の評価＞
得られたスエード調人工皮革にて、ゴルフ手袋を縫製して、５人のパネラーが着用評価して風合い評価を実施した。
○：柔軟な風合い、フィット感が良好
△：やや風合いが硬く、ややフィット感不足
×：風合いが硬く、フィット感不良
Next, embodiments of the present invention will be described with specific examples, but the present invention is not limited to these examples. In the examples, “part” and “%” relate to mass unless otherwise specified.
<Fineness measuring method>
The cross section of the fiber bundle of the base material for artificial leather was magnified 2000 times with an electron microscope and photographed. The diameter of the ultrafine fiber was measured for any three ultrafine fiber bundles, and the specific gravity of the polymer constituting the island component was long. The fineness and average fineness of the ultrafine fiber were calculated by calculating the weight of 10,000 m.
<Measurement method of exposure ratio of island components>
The cross section of the released yarn collected at the time of spinning is magnified 1000 times with an electron microscope and photographed. As shown in FIG. 2, in the cross section of the sea-island fiber, the outer peripheral length of each island component (X ) And the circumference (Y) of the portion exposed from the sea component of the sea-island fiber at the outer periphery of the island component, respectively, and the average value of (Y) / (X) is calculated. It calculated | required from the average value of (Y) / (X) computed in the sea-island type | mold fiber.
<Evaluation of texture>
Golf gloves were sewed on the obtained suede-like artificial leather, and five panelists evaluated wearing and evaluated the texture.
○: Soft texture, good fit △: Slightly hard texture, slightly lack of fit ×: Hard texture, poor fit
島成分としてナイロン６を６５部と海成分としてポリエチレンを３５部とをそれぞれ別のエクストルーダーで溶融し、両者を紡糸口金部で繊維形状を規定して合流させ紡糸する方法において、海島型繊維の外周に配置された島成分が、海島型繊維の外周に露出するように流路を規制したノズルパックを用いて溶融紡糸して、紡糸後の繊維断面においてポリエチレンからなる海成分中にナイロン６からなる２５個の島成分がほぼ均一に配置された繊度１０デシテックスの海島型繊維を得た。尚、得られた海島型繊維の横断面において、海島型繊維の外周部に配置された島成分の外周長の約２０％が海島型繊維の表面に露出するように、島成分と海成分との紡糸温度における溶融粘度バランスを調整した。
得られた海島型繊維を３.０倍に延伸し、捲縮を付与した後、繊維長５１ｍｍに切断してステープルとし、これをカードで解繊した後、クロスラップウェバーでウェブとした。次に、得られたウェブを積層して、バーブのあるニードルを厚さ方向に貫通させるニードルパンチ絡合法によりステープルを厚さ方向に絡合させて、目付６５０ｇ／ｍ２の絡合不織布とした。尚、延伸後からニードルパンチ絡合処理までの工程の間に、繊維は徐々に自発の収縮を生じており、繊維の繊度は約４．５デシテックスになっていた。この絡合不織布に、ポリエーテル系ポリウレタンを主体とするポリウレタン組成物１３部、ジメチルホルムアミド（以下ＤＭＦと称す。）８７部の組成液を含浸し、水中で湿式凝固させ、さらに水洗することでＤＭＦを除去した後、海島型繊維ステープル中のポリエチレンからなる海成分を加熱したトルエン中で抽出除去し、次いで熱水浴中でトルエンを除去し、乾燥して、ナイロン６の極細繊維からなる束状繊維とポリウレタンとからなる厚さ約１.３ｍｍの人工皮革用基材を得た。
In a method in which 65 parts of nylon 6 as an island component and 35 parts of polyethylene as a sea component are melted with different extruders, and both are spun together by defining the fiber shape at the spinneret and spinning. From the nylon 6 into the sea component made of polyethylene in the fiber cross section after spinning, melt-spinning is performed using a nozzle pack in which the flow path is regulated so that the island component arranged on the outer periphery is exposed to the outer periphery of the sea-island fiber. A sea island type fiber having a fineness of 10 dtex was obtained. In addition, in the cross section of the obtained sea-island type fiber, the island component and the sea component are arranged so that about 20% of the outer peripheral length of the island component arranged on the outer periphery of the sea-island type fiber is exposed on the surface of the sea-island type fiber. The melt viscosity balance at the spinning temperature was adjusted.
The obtained sea-island type fiber was stretched 3.0 times and crimped, then cut into a fiber length of 51 mm to form a staple, which was defibrated with a card and then made into a web with a cross wrap webber. Next, the obtained web was laminated, and the staple was entangled in the thickness direction by a needle punch entanglement method in which a needle with a barb penetrated in the thickness direction to obtain an entangled nonwoven fabric having a basis weight of 650 g / m 2 . . In addition, during the process from drawing to needle punch entanglement treatment, the fibers gradually contracted spontaneously, and the fineness of the fibers was about 4.5 dtex. The entangled nonwoven fabric was impregnated with a composition solution of 13 parts of a polyurethane composition mainly composed of polyether polyurethane and 87 parts of dimethylformamide (hereinafter referred to as DMF), wet coagulated in water, and further washed with water to obtain DMF. After removing the water, the sea component composed of polyethylene in the sea-island fiber staple is extracted and removed in heated toluene, then the toluene is removed in a hot water bath and dried to form a bundle of ultrafine nylon 6 fibers. A base material for artificial leather having a thickness of about 1.3 mm made of fiber and polyurethane was obtained.
この人工皮革用基材の繊維束の断面を電子顕微鏡で２０００倍に拡大して写真に撮り観察すると、極細繊維の平均繊度は０.２７デシテックスで、かつ繊度のばらつきは殆ど認められなかった。また、人工皮革用基材内部のポリウレタンと極細繊維束の少なくとも一部分以上が接着している部分を観察すると、接着している極細繊維束の最外周に配置された極細繊維は高分子弾性体と接着しているが、最外周以外の極細繊維は高分子弾性体と接着していない状態が認められた。
この人工皮革用基材をスライスにより厚さ方向に二分割して、分割後の面をサンドペーパーでバフィング処理して厚さ０．６０ｍｍに厚み合わせを行なった後、他の面をサンドペーパーをセットしたエメリーバフ機で起毛兼整毛の効果のあるバフィング処理を施して極細繊維立毛面を形成し、さらにIrgalan Red 2GL(Chiba Geigy)を用いて、４％ｏｗｆの濃度で染色した。染色後にブラッシングして整毛仕上げをしてスエード調人工皮革を得た。得られたスエード調人工皮革は、その十数か所の断面を電子顕微鏡で５００倍に拡大して写真に撮り観察したところ、観察された極細繊維束のうちで、高分子弾性体が隣接して存在している極細繊維束では、最外周に配置された極細繊維束を４箇所観察した結果、１極細繊維束当り平均１１本の極細繊維が高分子弾性体に接着しており、それ以外の極細繊維は高分子弾性体と接着していない状態であり、また、極細繊維束の内部での高分子弾性体の存在は認められなかった。得られたスエード調人工皮革は耐ピリング性に極めて優れたものであり、さらに発色性、外観、手触り、風合い共に極めて良好なものであった。ＪＩＳ Ｌ１０７６ Ａ法（２０時間）にて測定した耐ピリング性と５人のパネラーにて評価した風合いの評価結果を表１に示す。
When the cross section of the fiber bundle of the base material for artificial leather was magnified 2000 times with an electron microscope and photographed and observed, the average fineness of the ultrafine fibers was 0.27 dtex, and variations in fineness were hardly recognized. In addition, when observing a portion where at least a part of the polyurethane and the ultrafine fiber bundle are bonded to each other in the base material for artificial leather, the ultrafine fibers arranged on the outermost periphery of the bonded ultrafine fiber bundle are the polymer elastic body and Although it was bonded, it was recognized that the ultrafine fibers other than the outermost periphery were not bonded to the polymer elastic body.
This artificial leather substrate is divided into two in the thickness direction by slicing, and the divided surface is buffed with sandpaper to adjust the thickness to 0.60 mm, and then the other surface is sandpaper. The emery buffing machine was used to perform buffing treatment with the effect of raising and trimming to form an ultrafine fiber raised surface, and further dyed at a concentration of 4% owf using Irgalan Red 2GL (Chiba Geigy). After dyeing, it was brushed and finished with hair to obtain a suede-like artificial leather. The obtained suede-like artificial leather was magnified 500 times with an electron microscope and photographed and observed, and among the observed ultrafine fiber bundles, a polymer elastic body was adjacent. As a result of observing four ultrafine fiber bundles arranged on the outermost periphery, an average of 11 ultrafine fibers per ultrafine fiber bundle is bonded to the polymer elastic body. The ultrafine fibers were not bonded to the polymer elastic body, and the presence of the polymer elastic body was not observed inside the ultrafine fiber bundle. The obtained suede-like artificial leather was extremely excellent in pilling resistance, and was very good in terms of color development, appearance, texture and texture. Table 1 shows the evaluation results of the pilling resistance measured by JIS L1076 A method (20 hours) and the texture evaluated by five panelists.
比較例１
海島型繊維の外周に配置された島成分が、内部の島成分と同様に海成分に被覆されるように流路を規制したノズルパックを用いて溶融紡糸して、海島型繊維の外周に配置された島成分の海島型繊維の表面への露出が無く、海成分にほぼ均一に覆われている海島型繊維を溶融紡糸して使用し、また、分割面とは別の面をサンドペーパーで起毛した後に、ＤＭＦ１０％、シクロヘキサノン９０％よりなる溶液を２０ｇ／ｍ２となるようにグラビア塗布し立毛を固定した以外は、実施例１と同様の手順にて、人工皮革用基材を作成し、さらにはスエード調人工皮革を作成した。
得られたスエード調人工皮革は、その十数か所の断面を電子顕微鏡で５００倍に拡大して写真に撮り観察したところ、観察された極細繊維束のうちで、表面付近では、わずかに高分子弾性体と極細繊維が接着している部分が認められたが、人工皮革用基材内部の高分子弾性体に包囲された極細繊維束では、最外周に配置された極細繊維と高分子弾性体との接着は認められず、発色性、外観、手触り、風合いは良好であったが、耐ピリング性に劣るものであった。
Comparative Example 1
The island component placed on the outer periphery of the sea-island fiber is melt-spun using a nozzle pack that regulates the flow path so that it is covered with the sea component in the same way as the inner island component, and placed on the outer periphery of the sea-island fiber. The sea island type fiber is not exposed to the surface of the sea island type fiber, and the sea island type fiber covered almost uniformly with the sea component is melt-spun and used, and the other side than the split surface is sandpaper. A base material for artificial leather was prepared in the same procedure as in Example 1 except that after raising, a nail was fixed by applying a gravure solution of 10% DMF and 90% cyclohexanone to 20 g / m 2. Furthermore, a suede-like artificial leather was created.
The obtained suede-like artificial leather was magnified 500 times with an electron microscope and photographed and observed, and among the observed ultrafine fiber bundles, it was slightly higher near the surface. A part where the molecular elastic body and the ultrafine fiber are bonded was observed. However, in the ultrafine fiber bundle surrounded by the polymer elastic body inside the base material for artificial leather, the ultrafine fiber placed on the outermost periphery and the polymer elastic Adhesion with the body was not observed, and the color development, appearance, touch and texture were good, but the pilling resistance was poor.
比較例２
島成分としてナイロン６を６５部と海成分としてポリスチレンを３５部とをそれぞれ別のエクストルーダーで溶融し、両者を比較例１で用いたノズルパックを用いて、紡糸口金部で繊維形状を規定して合流させ紡糸する方法により溶融紡糸して、紡糸後の繊維断面においてポリエチレンからなる海成分中にナイロン６からなる２５個の島成分がほぼ均一に配置された繊度１０デシテックスの海島型繊維を得た。尚、得られた海島型繊維の外周に配置された島成分の海島型繊維の表面への露出が無く、海成分にほぼ均一に覆われていた。
得られた海島型繊維を３.０倍に延伸し、捲縮を付与した後、繊維長５１ｍｍに切断してステープルとし、これをカードで解繊した後、クロスラップウェバーでウェブとした。次に、得られたウェブを積層して、バーブのあるニードルを厚さ方向に貫通させるニードルパンチ絡合法によりステープルを厚さ方向に絡合させて、目付６５０ｇ／ｍ２の絡合不織布とした。尚、延伸後からニードルパンチ絡合処理までの工程の間に、繊維は徐々に自発の収縮を生じており、繊維の繊度は約４．１デシテックスになっていた。この絡合不織布に、２０％ＰＶＡ水溶液を絡合不織布の質量に対して６０％程度の割合で含浸した後に乾燥し、さらに海島型繊維ステープル中のポリスチレンからなる海成分を加熱したトルエン中で抽出除去し、次いでトルエンを除去し、乾燥した。その後、ポリエーテル系ポリウレタンを主体とするポリウレタン組成物１３部、ＤＭＦ８７部の組成液を含浸し、水中で湿式凝固させ、さらに水洗、乾燥することでＤＭＦを除去した後、乾燥して、ナイロン６の極細繊維からなる束状繊維とポリウレタン組成物とからなる厚さ約１.３ｍｍの人工皮革用基材を得た。
Comparative Example 2
65 parts of nylon 6 as the island component and 35 parts of polystyrene as the sea component were melted with different extruders, and both were used to define the fiber shape at the spinneret using the nozzle pack used in Comparative Example 1. The melt-spinning is performed by a method of joining and spinning to obtain a sea-island fiber having a fineness of 10 dtex, in which 25 island components made of nylon 6 are arranged almost uniformly in a sea component made of polyethylene in the cross section of the spun fiber. It was. In addition, there was no exposure to the surface of the sea-island type fiber of the island component arrange | positioned on the outer periphery of the obtained sea-island type fiber, and it was covered with the sea component substantially uniformly.
The obtained sea-island type fiber was stretched 3.0 times and crimped, then cut into a fiber length of 51 mm to form a staple, which was defibrated with a card and then made into a web with a cross wrap webber. Next, the obtained web was laminated, and the staple was entangled in the thickness direction by a needle punch entanglement method in which a needle with a barb penetrated in the thickness direction to obtain an entangled nonwoven fabric having a basis weight of 650 g / m 2 . . In addition, during the process from drawing to needle punch entanglement treatment, the fibers gradually contracted spontaneously, and the fineness of the fibers was about 4.1 dtex. The entangled nonwoven fabric is impregnated with a 20% PVA aqueous solution at a ratio of about 60% with respect to the mass of the entangled nonwoven fabric, dried, and further extracted with toluene in a sea component made of polystyrene in sea-island fiber staples. Removed, then removed toluene and dried. Thereafter, 13 parts of a polyurethane composition mainly composed of polyether polyurethane and 87 parts of DMF were impregnated, wet coagulated in water, further washed with water and dried to remove DMF, and then dried to obtain nylon 6 A base material for artificial leather having a thickness of about 1.3 mm made of a bundle of ultrafine fibers and a polyurethane composition was obtained.
この人工皮革用基材の繊維束の断面を電子顕微鏡で２０００倍に拡大して写真に撮り観察すると、極細繊維の平均繊度は０.２５デシテックスで、かつ繊度のばらつきは殆ど認められなかった。
この人工皮革用基材をスライスにより厚さ方向に二分割して、分割後の面をサンドペーパーでバフィング処理して厚さ０．６０ｍｍに厚み合わせを行なった後、他の面をサンドペーパーをセットしたエメリーバフ機で起毛兼整毛の効果のあるバフィング処理を施して極細繊維立毛面を形成し、さらにIrgalan Red 2GL(Chiba Geigy)を用いて、４％ｏｗｆの濃度で染色した。染色後にブラッシングして整毛仕上げをしてスエード調人工皮革を得た。得られたスエード調人工皮革は、その十数か所の断面を電子顕微鏡で５００倍に拡大して写真に撮り観察したところ、観察された極細繊維束のうちで、高分子弾性体に包囲された極細繊維束では、最外周に配置された極細繊維のみならず、極細繊維束の内部においても多くの極細繊維と高分子弾性体との間に接着が認められる状態であり、耐ピリング性に極めて優れたものであったが、ざらざらとした触感を有し、硬めの風合いであり、良好なスエードは得られなかった。
When the cross section of the fiber bundle of the artificial leather substrate was magnified 2000 times with an electron microscope and photographed and observed, the average fineness of the ultrafine fibers was 0.25 dtex, and almost no variation in fineness was observed.
This artificial leather substrate is divided into two in the thickness direction by slicing, and the divided surface is buffed with sandpaper to adjust the thickness to 0.60 mm, and then the other surface is sandpaper. The emery buffing machine was used to perform buffing treatment with the effect of raising and trimming to form an ultrafine fiber raised surface, and further dyed at a concentration of 4% owf using Irgalan Red 2GL (Chiba Geigy). After dyeing, it was brushed and finished with hair to obtain a suede-like artificial leather. The obtained suede-like artificial leather was magnified 500 times with an electron microscope and photographed and observed, and among the observed ultrafine fiber bundles, it was surrounded by a polymer elastic body. In the ultrafine fiber bundle, not only the ultrafine fibers arranged on the outermost circumference, but also the inside of the ultrafine fiber bundle is in a state where adhesion between many ultrafine fibers and the polymer elastic body is recognized, and the pilling resistance is improved. Although it was extremely excellent, it had a rough feel and a hard texture, and a good suede could not be obtained.
本発明で得られたスエード調人工皮革は、外観、風合いが良好で、かつ発色性と耐ピリング性に優れたものであり、衣料用、靴用、袋物用、家具用、カーシート用、ゴルフ手袋等の各種スポーツ手袋用として利用できる。 The suede-like artificial leather obtained in the present invention has a good appearance and texture, and has excellent color development and pilling resistance. For clothing, shoes, bags, furniture, car seats, golf It can be used for various sports gloves such as gloves.
Claims (3)
（Ｉ）海島型繊維の横断面において、海島型繊維の外周に配置された島成分の外周長の５％から３０％が、海島型繊維の外周表面に露出している海島型繊維からなる絡合不織布を製造する工程、
（ＩＩ）該絡合不織布の内部に高分子弾性体を付与する工程、
（ＩＩＩ）海島型繊維を極細繊維束に変性する工程
を順次行うことを特徴とする人工皮革用基材の製造方法。 When manufacturing a base material for artificial leather in which a polymer elastic body is contained in an entangled nonwoven fabric made of a bundle of ultrafine fibers in which 10 to 250 ultrafine fibers of 0.01 to 0.3 decitex are bundled,
(I) In the cross section of the sea-island type fiber, a tangle of sea-island type fibers in which 5% to 30% of the outer circumference length of the island component arranged on the outer circumference of the sea-island type fiber is exposed on the outer circumferential surface of the sea-island type fiber A process for producing a synthetic nonwoven fabric,
(II) providing a polymer elastic body in the entangled nonwoven fabric;
(III) A method for producing a base material for artificial leather, comprising sequentially performing a step of modifying sea-island type fibers into ultrafine fiber bundles.
A suede-like artificial leather having napped fibers made of ultrafine fibers formed on at least one surface of the artificial leather substrate according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222770A (en) * | 2009-02-27 | 2010-10-07 | Kuraray Co Ltd | Artificial leather and method for producing the same |
| JP2011074541A (en) * | 2009-09-30 | 2011-04-14 | Kuraray Co Ltd | Napped artificial leather having excellent pilling resistance |
| WO2022097579A1 (en) * | 2020-11-05 | 2022-05-12 | 株式会社クラレ | Napped artificial leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256460A (en) * | 1998-03-13 | 1999-09-21 | Kuraray Co Ltd | Production of nonwoven fabric |
| JP2005220461A (en) * | 2004-02-04 | 2005-08-18 | Toray Ind Inc | Sheet-like product |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256460A (en) * | 1998-03-13 | 1999-09-21 | Kuraray Co Ltd | Production of nonwoven fabric |
| JP2005220461A (en) * | 2004-02-04 | 2005-08-18 | Toray Ind Inc | Sheet-like product |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222770A (en) * | 2009-02-27 | 2010-10-07 | Kuraray Co Ltd | Artificial leather and method for producing the same |
| JP2011074541A (en) * | 2009-09-30 | 2011-04-14 | Kuraray Co Ltd | Napped artificial leather having excellent pilling resistance |
| WO2022097579A1 (en) * | 2020-11-05 | 2022-05-12 | 株式会社クラレ | Napped artificial leather |
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