JP4156479B2 - Method for impregnating polymer elastic water dispersion and method for producing artificial leather substrate using the same - Google Patents
Method for impregnating polymer elastic water dispersion and method for producing artificial leather substrate using the same Download PDFInfo
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本発明は水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維から構成された繊維絡合体へ高分子弾性体水分散液を含浸する際に、繊維絡合体に対する高分子弾性体水分散液の浸透性と含浸圧力等を調整することで、水溶性高分子の溶出、シワや伸びの発生、あるいは生産効率の低下を生じることなく該繊維絡合体の内部に高分子弾性体水分散液を含浸する方法およびそれを用いた人工皮革基体の製造方法を提供するものである。 The present invention relates to a polymer elastic body for a fiber entangled body when impregnated with an aqueous dispersion of a polymer elastic body into a fiber entangled body composed of ultrafine fiber generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component. By adjusting the permeability of the aqueous dispersion, the impregnation pressure, etc., the polymer elastic body water is contained in the fiber entangled body without causing elution of water-soluble polymer, generation of wrinkles or elongation, or reduction of production efficiency. A method for impregnating a dispersion and a method for producing an artificial leather substrate using the same are provided.
従来から、不織布、織編物などの繊維絡合体およびこれらの各種加工品などの厚手のシート状物にポリウレタン等で代表される弾性重合体溶液、エマルジョンなどの高分子弾性体分散液を含浸し、皮革様の風合いの付与、さらには機能性の優れたシート状物を作製することは良く知られており、工業的にも広く活用されている。
また近年、有機溶剤の使用に対して人体、環境への悪影響の懸念から、人工皮革の製造においても無溶剤での製造プロセスの確立が要望されており、例えば、繊維絡合体に用いる極細繊維発生型繊維としては水溶液で抽出成分を抽出除去して極細繊維とするタイプが、また繊維絡合体の内部に含浸する樹脂としては高分子弾性体水分散液が検討されており、それらの組み合せの製造プロセスが挙げられる。また極細繊維発生型繊維として公知の剥離分割型タイプを用いる場合においても、形態安定性、高分子弾性体からの立毛層保護など風合い、品位を制御するといった目的からポリビニルアルコールを予め繊維絡合体に付与し、その後、さらに高分子弾性体水分散液を含浸する等の組み合せによる製造プロセスが挙げられる。しかしながらこれら組み合せ製造プロセスを用いた場合、ポリビニルアルコールが高分子弾性体水分散液の溶媒中へ溶出し、高分子弾性体水分散液を汚染してしまうといった問題を抱えている。
Conventionally, fiber entanglements such as nonwoven fabrics and woven and knitted fabrics and thick sheet-like materials such as these various processed products are impregnated with an elastic polymer solution represented by polyurethane and the like, and a polymer elastic dispersion such as an emulsion, It is well known to impart a leather-like texture and to produce a sheet-like material having excellent functionality, and it is widely used industrially.
In recent years, due to concerns about adverse effects on the human body and the environment due to the use of organic solvents, there has been a demand for the establishment of a solvent-free manufacturing process in the production of artificial leather. As the type fiber, there is a type in which the extracted components are extracted and removed with an aqueous solution to form ultrafine fibers, and as the resin impregnated inside the fiber entangled body, an elastic polymer aqueous dispersion is being studied, and the combination thereof is manufactured. Process. In addition, even when using a well-known peeled split type as an ultrafine fiber generating fiber, polyvinyl alcohol is preliminarily formed into a fiber entangled body for the purpose of controlling the texture and quality such as form stability, napping layer protection from a polymer elastic body, etc. And a production process by a combination of impregnation with an aqueous dispersion of a polymer elastic body. However, when these combined production processes are used, there is a problem that polyvinyl alcohol is eluted into the solvent of the polymer elastic water dispersion and contaminates the polymer elastic water dispersion.
例えば、従来の含浸方法としては、走行している繊維絡合体を高分子弾性体溶液中へ浸漬した後、ニップ装置で絞ることにより繊維絡合体内部の空気を追出し高分子弾性体溶液と置換させる方法、さらには適当なニップ圧力を採用することにより所望の含浸率で含浸する方法（例えば、特許文献１参照。）が提案されている。しかしながら、この方法で繊維絡合体内部に充分含浸液を含浸させるためにはニップ装置が複数段配列された多段ニップ装置で処理するか、あるいは単一のニップ装置であれば複数回のニップ処理を要しなければならず、この過程でのシワ、永久の伸びなどが問題となる他、多段ニップ装置の場合には設備費が高価になり、単一のニップ装置による複数回のニップ処理を行う場合には複数回の処理に要する手間により生産効率が悪くなる。また水溶性高分子成分を有する繊維からなる繊維絡合体へ高分子弾性体水分散液を含浸する場合、ニップ処理することで繊維中の水溶性高分子成分が搾り出され、高分子弾性体水分散液が汚染されて該高分子弾性体水分散液の品質が不安定となるといった問題も生じる。 For example, as a conventional impregnation method, after the running fiber entangled body is immersed in the polymer elastic body solution, the air inside the fiber entangled body is expelled by the nip device and replaced with the polymer elastic body solution. A method of impregnating at a desired impregnation rate by adopting a suitable nip pressure (for example, see Patent Document 1) has been proposed. However, in order to sufficiently impregnate the impregnating liquid inside the fiber entangled body by this method, processing is performed with a multi-stage nip apparatus in which a plurality of nip apparatuses are arranged, or if a single nip apparatus is used, a plurality of nip processes are performed. In addition to problems such as wrinkles and permanent elongation in this process, in the case of a multi-stage nip apparatus, the equipment cost becomes expensive, and multiple nip processes are performed by a single nip apparatus. In some cases, the production efficiency deteriorates due to the time and effort required for a plurality of processes. Further, when impregnating a fiber entangled body composed of fibers having a water-soluble polymer component with a polymer elastic body aqueous dispersion, the water-soluble polymer component in the fiber is squeezed out by nip treatment, so that the polymer elastic body water There is also a problem that the dispersion is contaminated and the quality of the polymer elastic water dispersion becomes unstable.
また、含浸時のシワや伸びの発生などの問題点を改善する方法として、繊維絡合体の厚さと同程度又はそれよりも幾分大きい間隙を有する一対の複数組のローラー間を通過させ、ローラー表面に均斉にかつ定常的に高分子弾性体分散液を供給することによって繊維絡合体内部へ該高分子弾性体分散液を含浸させる方法（例えば、特許文献２参照。）が提案されている。この方法では、繊維絡合体がローラーを通過するときのローラーによる加圧力が含浸の推進力となり、必要以上に強い力で圧縮しないため繊維絡合体のシワ、伸びの発生を防ぐことができる。しかしながら、各ローラー１本当たりの通過時間は０．１〜０．２秒程度の極めて短時間であるため、含浸を充分に行うために多数のローラーが必要となり、コスト的、スペース的に好ましくなく工業的に不利である。また水溶性高分子成分を有する繊維からなる繊維絡合体へ高分子弾性体水分散液を含浸する場合、ローラーが必要以上に強い力で圧縮しないものの、該繊維絡合体がローラーと接触する頻度や時間が長くなればなるほど、すなわち該繊維絡合体が高分子弾性体水分散液へ接触する時間が長くなればなるほど、繊維を構成する水溶性高分子成分の溶出が懸念され、やはり高分子弾性体水分散液が汚染されやすいといった問題が生じる。 Further, as a method of improving problems such as wrinkles and elongation at the time of impregnation, the roller is passed between a plurality of pairs of rollers having a gap that is the same as or slightly larger than the thickness of the fiber entanglement. There has been proposed a method (for example, refer to Patent Document 2) in which the elastic polymer dispersion is impregnated into the fiber entangled body by supplying the elastic polymer dispersion uniformly and constantly on the surface. In this method, the pressure applied by the roller when the fiber entangled body passes the roller becomes a driving force for impregnation, and the fiber entangled body can be prevented from being wrinkled and stretched because it is not compressed with a force stronger than necessary. However, since the passing time per roller is an extremely short time of about 0.1 to 0.2 seconds, a large number of rollers are required for sufficient impregnation, which is not preferable in terms of cost and space. It is industrially disadvantageous. Also, when impregnating a polymer elastic body aqueous dispersion into a fiber entangled body composed of fibers having a water-soluble polymer component, although the roller does not compress with an excessively strong force, the frequency at which the fiber entangled body contacts the roller, The longer the time, that is, the longer the time for which the fiber entangled body is in contact with the aqueous dispersion of the polymer elastic body, there is a concern about the elution of the water-soluble polymer component constituting the fiber. There arises a problem that the aqueous dispersion is easily contaminated.
また、ローラーによるニップ処理を行わない方法、あるいは多段ローラーを使用せずに含浸する方法として、走行している繊維絡合体に対して片面、もしくは両面から加圧液体を圧入することにより含浸させる方法（例えば、特許文献３および特許文献４参照。）が提案されている。しかしながらこれらの方法では、繊維絡合体内の厚さ方向に均一に含浸液が含浸しないうちに繊維絡合体が通過してしまい、充分に含浸液を含浸させるには繊維絡合体の反対側から更に吸引するか、処理速度を落とさなければならず、設備が複雑になるばかりか液体の含浸に比較的長時間を要し、生産効率を低下させるといった問題がある。
さらに、厚手の繊維絡合体に含浸処理する場合に含浸する液体の圧入圧力を上げると、繊維絡合体と含浸装置との境界面から含浸液が漏出してしまうなどの問題がある。
Also, as a method of not performing the nip treatment with a roller or a method of impregnation without using a multistage roller, a method of impregnating a traveling fiber entangled body by pressurizing a pressurized liquid from one side or both sides (For example, refer to
Furthermore, when the press-fitting pressure of the liquid to be impregnated is increased when impregnating the thick fiber entangled body, there is a problem that the impregnating liquid leaks from the interface between the fiber entangled body and the impregnation apparatus.
更に前記した問題点を改善する方法として、加圧された高分子弾性体溶液を繊維絡合体の片面から厚さ方向の途中まで含浸させ、次いで該溶液が途中まで含浸された繊維絡合体をさらにニップロールで加圧処理して、繊維絡合体の厚さ方向全体に液体を含浸させる含浸方法（例えば、特許文献５参照。）が提案されている。この方法は処理速度を落とすことなく繊維絡合体の内部へ均一に含浸することが可能であり、またニップ処理を行うものの余剰含浸液が発生しない含浸方法である。しかしながら、水溶性高分子成分を有する極細繊維発生型繊維からなる繊維絡合体へ高分子弾性体水分散液を含浸する場合、ニップロール処理で該水溶性高分子成分が繊維絡合体外部へ搾り出されないまでも繊維絡合体内部へ搾り出されてしまう傾向がある。このような含浸状態で人工皮革を製造する場合、高分子弾性体が極細繊維を直接バインドする傾向がありそれによって風合いが硬く損なわれてしまう。 Further, as a method for improving the above-described problems, a pressurized polymer elastic body solution is impregnated from one side of the fiber entangled body to the middle in the thickness direction, and then the fiber entangled body impregnated with the solution halfway is further added. An impregnation method (for example, refer to Patent Document 5) in which liquid is impregnated in the entire thickness direction of a fiber entangled body by pressurizing with a nip roll has been proposed. This method is capable of uniformly impregnating the inside of the fiber entangled body without reducing the processing speed, and is an impregnation method in which an excess impregnation liquid is not generated although nip treatment is performed. However, when a polymer elastic body aqueous dispersion is impregnated into a fiber entanglement made of ultrafine fiber-generating fibers having a water-soluble polymer component, the water-soluble polymer component is not squeezed out of the fiber entanglement by nip roll treatment. It tends to be squeezed into the fiber entangled body. When artificial leather is produced in such an impregnated state, the polymer elastic body tends to bind the ultrafine fibers directly, and the texture is hard and damaged.
以上、従来の含浸技術では、水溶性高分子成分を有する極細繊維発生型繊維からなる繊維絡合体へ高分子弾性体水分散液を含浸する場合において、極細繊維発生型繊維を構成する水溶性高分子成分の溶出、繊維絡合体のシワや伸びの発生、あるいは生産効率が低下することなく含浸すること、さらには人工皮革を製造することができなかった。
本発明は水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維から構成されている繊維絡合体へ高分子弾性体水分散液を含浸させるに際し、繊維絡合体に対する高分子弾性体水分散液の浸透性と含浸圧力を調整することで、水溶性高分子成分の溶出、シワ、伸びの発生、さらには生産効率の低下を生じることなく含浸する方法を提供するものである。 The present invention provides a polymer elastic body for a fiber entangled body when impregnating a fiber entangled body composed of ultrafine fiber generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component with a polymer elastic body aqueous dispersion. By adjusting the permeability and impregnation pressure of the aqueous dispersion, there is provided a method of impregnation without causing elution, wrinkles and elongation of the water-soluble polymer component, and further without lowering the production efficiency.
すなわち、本発明は水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維から構成されている繊維絡合体の内部に高分子弾性体水分散液を含浸させるに際し、以下（１）〜（５）を満足することを特徴とする高分子弾性体水分散液の含浸方法である。
（１）高分子弾性体水分散液をポンプを設けて加圧することにより、繊維絡合体の内部に該高分子弾性体水分散液を加圧浸透させることを利用した含浸方法であること
（２）繊維絡合体への浸透時間を１０秒以下に調節した高分子弾性体水分散液を用いること
（３）高分子弾性体水分散液の含浸圧力が１，０００〜１００，０００Ｐａであること
（４）繊維絡合体が含浸直前に繊維絡合体厚みの４０〜９９％の間隙で圧縮されていること
（５）高分子弾性体水分散液供給量が繊維絡合体空隙量の６０〜１００％であること
さらには、極細繊維発生型繊維を構成する水溶性高分子成分が、炭素数４以下のオレフィン単位および／またはビニルエーテル単位を１〜２０モル％含有し、けん化度９０〜９９．９９モル％である変性ポリビニルアルコールであることが好ましい。
また、上記含浸方法により繊維絡合体の内部に高分子弾性体水分散液を含浸した後、該高分子弾性体を加熱凝固し、さらに極細繊維発生型繊維を構成する水溶性高分子成分を６０〜１００℃の熱水で抽出除去し極細繊維化することを特徴とする人工皮革基体の製造方法であり、人工皮革基体を構成する高分子弾性体と極細繊維化された繊維絡合体の比率が１５：８５〜６０：４０の範囲となるように含浸することが好ましい。
That is, when the present invention impregnates a polymer elastic water dispersion into the inside of a fiber entangled body composed of ultrafine fiber generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component, the following (1) It is an impregnation method of the polymer elastic body aqueous dispersion characterized by satisfying (5).
(1) An impregnation method using pressurizing and penetrating the polymer elastic water dispersion into the fiber entangled body by pressurizing the polymer elastic water dispersion with a pump (2 ) Use a polymer elastic water dispersion whose penetration time into the fiber entangled body is adjusted to 10 seconds or less. (3) The impregnation pressure of the polymer elastic water dispersion is 1,000 to 100,000 Pa ( 4) The fiber entangled body is compressed in a gap of 40 to 99% of the fiber entangled body thickness immediately before impregnation. (5) The polymer elastic body aqueous dispersion supply amount is 60 to 100% of the fiber entangled body void amount. Furthermore, the water-soluble polymer component constituting the ultrafine fiber generating fiber contains 1 to 20 mol% of an olefin unit and / or vinyl ether unit having 4 or less carbon atoms, and a saponification degree of 90 to 99.99 mol%. Modified polyvinylalco It is preferably Le.
Also, after impregnating the inside of the fiber entangled body with the polymer elastic body aqueous dispersion by the above impregnation method, the polymer elastic body is heated and coagulated, and further the water-soluble polymer component constituting the ultrafine fiber generating fiber is added. A method for producing an artificial leather substrate, which is extracted and removed with hot water at -100 ° C. to form an ultrafine fiber, wherein the ratio of the polymer elastic body constituting the artificial leather substrate to the ultrafine fiber entanglement is It is preferable to impregnate so that it may become the range of 15: 85-60: 40.
本発明は、水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維から構成された繊維絡合体へ高分子弾性体水分散液を含浸する際に、該繊維絡合体に対する高分子弾性体水分散液の浸透性と含浸圧力を調整することで、水溶性高分子成分の溶出およびシワや伸びの発生がなく、また生産効率の低下を生じることなく含浸する方法、さらには皮革様で均一な風合いや優れた物性を有する人工皮革基体を安定に製造する方法を提供する。 When impregnating a fiber entangled body composed of ultrafine fiber generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component with a polymer elastic body aqueous dispersion, the present invention provides a polymer for the fiber entangled body. By adjusting the permeability and impregnation pressure of the elastic water dispersion, there is no elution of water-soluble polymer components, no wrinkles or elongation, and impregnation without reducing production efficiency. A method for stably producing an artificial leather substrate having a uniform texture and excellent physical properties is provided.
以下、本発明を詳細に説明する。
本発明は水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維から構成された繊維絡合体へ高分子弾性体水分散液を含浸する際に、該水溶性高分子成分の溶出、シワ、伸びの発生を抑制した含浸方法である。すなわち、繊維絡合体に対する高分子弾性体水分散液の浸透性と含浸圧力を調整することによって、含浸速度を低下させること無く、かつ過剰に加圧すること無く含浸させることが可能となる。また繊維絡合体を含浸直前に特定の圧縮を行うことによって、繊維絡合体内部の空気と高分子弾性体水分散液の置換および含浸量の制御が可能となり、さらに従来必要であったニップロールを用いなくとも皮革様の風合いや物性に適した所望の量の含浸および含浸状態が可能となる。また、高分子弾性体水分散液を繊維絡合体空隙量の６０〜１００％供給することで該繊維絡合体の内部へ均一に含浸することができる。
Hereinafter, the present invention will be described in detail.
The present invention provides an elution of a water-soluble polymer component when impregnating a fiber entangled body composed of ultrafine fiber-generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component with a polymer elastic body aqueous dispersion. It is an impregnation method that suppresses generation of wrinkles and elongation. That is, by adjusting the permeability and impregnation pressure of the polymer elastomer aqueous dispersion with respect to the fiber entangled body, the impregnation can be performed without reducing the impregnation speed and without excessively pressurizing. In addition, by performing specific compression immediately before impregnation of the fiber entangled body, it becomes possible to replace the air inside the fiber entangled body and the polymer elastic body aqueous dispersion and control the amount of impregnation, and furthermore, using a nip roll that was conventionally required At least, a desired amount of impregnation and impregnation state suitable for leather-like texture and physical properties are possible. Moreover, the inside of this fiber entanglement body can be uniformly impregnated by supplying the polymer elastic body aqueous dispersion 60 to 100% of the fiber entanglement void amount.
本発明の繊維絡合体を構成する極細繊維発生型繊維の繊度は特に人工皮革の用途によって任意に選択でき特に制限されるものではないが、極細繊維化後に０．０００１〜０．５デシテックスの繊度を有し、０．００１〜０．４５デシテックスの繊度を有することが好ましく、０．００２〜０．４デシテックスの繊度を有することが人工皮革基体を製造する上でより好ましい。
また本発明の水溶性高分子成分とは、該成分が水溶液により抽出除去される成分を示し、水難溶性高分子成分とは、該成分が水溶液により抽出除去されにくい成分を示す。そして、水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維は少なくとも１成分が水溶液による抽出処理で抽出除去されるものであれば、海島型複合繊維、混合紡糸型繊維などの多成分系複合繊維のいずれを使用してもよい。本発明で用いられる水溶性高分子成分としては、水溶液（水系溶剤と称することもある）で抽出処理できるポリマーであれば、公知のポリマーが使用できるが、水系溶剤で溶解可能なポリビニルアルコール共重合体類（以下ＰＶＡと略することもある）を用いることが好ましい。ＰＶＡは容易に熱水で溶解除去が可能であり、水系溶剤で抽出除去する際の収縮挙動によって極細繊維成分の極細繊維発生型繊維に構造捲縮が発現し、繊維絡合体が嵩高く緻密なものとなって非常に柔軟な天然皮革のような優れた風合いの人工皮革基体が得られる点、および抽出処理する際に極細繊維成分や高分子弾性体成分の分解反応が実質的に起こらないため極細繊維成分に用いる熱可塑性樹脂および高分子弾性体成分の限定が無い点、更には環境に配慮した点等から好適に用いられる。
The fineness of the ultrafine fiber generating fiber constituting the fiber entangled body of the present invention is not particularly limited and can be arbitrarily selected depending on the use of the artificial leather. However, the fineness of 0.0001 to 0.5 dtex after making the ultrafine fiber And preferably has a fineness of 0.001 to 0.45 dtex, and more preferably 0.002 to 0.4 dtex when producing an artificial leather substrate.
The water-soluble polymer component of the present invention refers to a component that is extracted and removed with an aqueous solution, and the poorly water-soluble polymer component refers to a component that is difficult to extract and remove with an aqueous solution. The ultrafine fiber generating fiber composed of a water-soluble polymer component and a poorly water-soluble polymer component can be used as long as at least one component can be extracted and removed by extraction with an aqueous solution. Any of multicomponent composite fibers may be used. As the water-soluble polymer component used in the present invention, any known polymer can be used as long as it can be extracted with an aqueous solution (sometimes referred to as an aqueous solvent). It is preferable to use a combination (hereinafter sometimes abbreviated as PVA). PVA can be easily dissolved and removed with hot water, and due to the shrinkage behavior when it is extracted and removed with an aqueous solvent, structural crimps appear in the ultrafine fiber-generating fiber of the ultrafine fiber component, and the fiber entanglement is bulky and dense. As a result, it is possible to obtain an artificial leather base with an excellent texture like natural leather, and because the decomposition reaction of ultrafine fiber components and polymer elastic body components does not occur substantially during extraction processing. The thermoplastic resin and polymer elastic body component used for the ultrafine fiber component are not limited, and are preferably used from the viewpoint of environmental considerations.
上記ＰＶＡはホモポリマーであっても共重合単位を導入した変性ポリビニルアルコールであってもよいが、溶融紡糸性、水溶性、繊維物性および抽出処理時の収縮特性などの観点から、共重合単位を導入したＰＶＡであることが好ましく、エチレン、プロピレン、１−ブテン、イソブテン等の炭素数４以下のα―オレフィン類、メチルビニルエーテル、エチレンビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル等のビニルエーテル類がより好ましい。また炭素数４以下のα−オレフィン類および／またはビニルエーテル類に由来する単位は、ＰＶＡ中に１〜２０モル％存在していることが好ましい。さらに、α−オレフィンがエチレンである場合において、繊維物性が高くなることから、特にエチレン単位が４〜１５モル％変成されたＰＶＡを使用することがより好ましい。
またけん化度は９０〜９９．９９モル％が好ましく、９２〜９９．９８モル％がより好ましく、９４〜９９．９６モル％がさらに好ましく、９５〜９９．９５モル％が特に好ましい。けん化度が９０モル％未満の場合には、ＰＶＡの熱安定性が悪く熱分解やゲル化によって満足な複合溶融紡糸を行うことができない。一方、けん化度が９９．９９モル％よりも大きいＰＶＡは安定に製造することが困難である。
また常温で水に溶出するタイプのＰＶＡを水溶性高分子成分として用いた場合には含浸時に水溶性高分子成分が溶出し高分子弾性体水分散液を汚染してしまう場合があり、また水溶性高分子成分の一部溶出に伴い極細繊維部分が露出することによって含浸した高分子弾性体が極細繊維を直接バインドし人工皮革の風合いが硬く損なわれやすいことから６０〜１００℃の熱水に溶出するタイプのＰＶＡを水溶性高分子成分として用いることが好ましい。さらに６０〜１００℃の熱水で水溶性高分子成分を溶出することによって、繊維絡合体の収縮挙動が発生し構造捲縮を生じやすいことから天然皮革並みの優れた風合いの人工皮革基体が得られる点で好ましい。
The PVA may be a homopolymer or a modified polyvinyl alcohol introduced with a copolymer unit. However, from the viewpoints of melt spinnability, water solubility, fiber properties, and shrinkage characteristics during extraction processing, the copolymer unit may be Preferably, the introduced PVA is an α-olefin having 4 or less carbon atoms such as ethylene, propylene, 1-butene, isobutene, methyl vinyl ether, ethylene vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether. More preferred are vinyl ethers such as Moreover, it is preferable that 1-20 mol% of units derived from α-olefins having 4 or less carbon atoms and / or vinyl ethers are present in PVA. Furthermore, when the α-olefin is ethylene, the fiber physical properties are improved, and therefore, it is more preferable to use PVA in which 4 to 15 mol% of ethylene units are particularly modified.
The saponification degree is preferably 90 to 99.99 mol%, more preferably 92 to 99.98 mol%, further preferably 94 to 99.96 mol%, and particularly preferably 95 to 99.95 mol%. When the saponification degree is less than 90 mol%, the thermal stability of PVA is poor and satisfactory composite melt spinning cannot be performed by thermal decomposition or gelation. On the other hand, PVA having a saponification degree larger than 99.99 mol% is difficult to produce stably.
In addition, when PVA of the type that elutes into water at room temperature is used as the water-soluble polymer component, the water-soluble polymer component may elute during impregnation and contaminate the polymer elastic water dispersion. Because the polymer elastic body impregnated by exposing the ultrafine fiber part due to partial elution of the functional polymer component directly binds the ultrafine fiber and the texture of the artificial leather is hard and easily damaged, the hot water at 60 to 100 ° C. It is preferable to use an elution type PVA as the water-soluble polymer component. Furthermore, by eluting the water-soluble polymer component with hot water at 60 to 100 ° C., the shrinkage behavior of the fiber entanglement occurs and the structure is easily crimped. This is preferable.
またＰＶＡを高温で紡糸すると紡糸性の悪化を招くため、本発明の水難溶性高分子成分としては公知の極細繊維となりうる、例えば、ポリアミド系、ポリエステル系およびポリオレフィン系等の成分であれば特に限定するものではない。そして、極細繊維を構成する水難溶性高分子成分の融点を適宜選択することが好ましく、極細繊維を構成する水難溶性高分子成分としては、極細繊維を形成する過程において抽出除去される水溶性高分子成分の融点プラス６０℃以下の融点を有する熱可塑性成分を選択することが極細繊維発生型繊維の紡糸安定性の点で好ましい。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、イソフタル酸を共重合したポリエチレンテレフタレートあるいはイソフタル酸を共重合したポリブチレンテレフタレートなどで代表されるポリエステル系樹脂、あるいはナイロン６、ナイロン１１、ナイロン１２などで代表されるポリアミド系樹脂が好ましく挙げられる。なお水溶性高分子成分の融点としては、紡糸性などの点から１６０〜２３０℃が好ましい。
そして必要に応じて、極細繊維中に顔料を０〜５質量％添加してもよく、この場合の顔料としては、例えばフタロシアニン系、アントラキノン系などの有機顔料や酸化チタン、カーボンブラック、クロムレッド、モリブデンレッドなどの無機顔料など通常ポリマー原着に使用されているものを用いることができる。顔料の添加方法としては、極細繊維を構成するポリマー中における顔料の分散性を良好にするため、極細繊維を構成するポリマーと顔料を押出機などのコンパウンド設備を用いて混練した後ペレット化したマスターバッチ方式を採用することが好ましい。また、極細繊維成分には本発明の目的や効果を損なわない範囲で、銅化合物などの安定剤、着色剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、難燃剤、可塑剤、潤滑剤、結晶化速度遅延剤を重合反応時、またはその後の工程で添加しても良い。微粒子の種類は特に限定されず、例えばシリカ、アルミナ、酸化チタン、炭酸カルシウム、硫酸バリウムなどの不活性微粒子を添加することができ、これらは単独で使用しても２種類以上併用しても良い。紡糸性、延伸性が向上する場合がある。
なお、極細繊維発生型繊維を構成する水溶性高分子成分と水難溶性高分子成分の質量比率としては、１０／９０〜６０／４０の範囲が、断面形成性が良好なため水溶性高分子が極細繊維を完全被覆しており、繊維絡合体内部での均一な浸透性が得られ均一含浸に有利である点、あるいは人工皮革基体とした場合、断面形成性が良好なため発生する極細繊維が均一であり、得られる人工皮革の風合いを損なわない点で好ましい。
In addition, since spinning of PVA at a high temperature causes deterioration of spinnability, the poorly water-soluble polymer component of the present invention can be a known ultrafine fiber. For example, it is particularly limited as long as it is a component such as polyamide, polyester and polyolefin Not what you want. The melting point of the poorly water-soluble polymer component constituting the ultrafine fiber is preferably selected as appropriate, and the poorly water-soluble polymer component constituting the ultrafine fiber is a water-soluble polymer extracted and removed in the process of forming the ultrafine fiber. It is preferable from the viewpoint of spinning stability of the ultrafine fiber generating fiber to select a thermoplastic component having a melting point of the component plus a melting point of 60 ° C. or less. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate copolymerized with isophthalic acid, polyester resin typified by polybutylene terephthalate copolymerized with isophthalic acid, or nylon 6, nylon 11, nylon 12, etc. Polyamide resins are preferred. The melting point of the water-soluble polymer component is preferably 160 to 230 ° C. from the viewpoint of spinnability.
If necessary, the pigment may be added in an amount of 0 to 5% by mass in the ultrafine fiber. In this case, examples of the pigment include organic pigments such as phthalocyanine and anthraquinone, titanium oxide, carbon black, chrome red, Inorganic pigments such as molybdenum red can be used that are usually used for polymer deposition. As a method for adding the pigment, in order to improve the dispersibility of the pigment in the polymer constituting the ultrafine fiber, the polymer and the pigment constituting the ultrafine fiber are kneaded using a compound facility such as an extruder and then pelletized. It is preferable to employ a batch method. In addition, a stabilizer such as a copper compound, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, and a plasticizer are included in the ultrafine fiber component as long as the purpose and effect of the present invention are not impaired. Further, a lubricant and a crystallization rate retarder may be added during the polymerization reaction or in the subsequent steps. The type of fine particles is not particularly limited, and for example, inert fine particles such as silica, alumina, titanium oxide, calcium carbonate, and barium sulfate can be added. These may be used alone or in combination of two or more. . Spinnability and stretchability may be improved.
The mass ratio of the water-soluble polymer component and the poorly water-soluble polymer component constituting the ultrafine fiber-generating fiber is in the range of 10/90 to 60/40. The ultra-fine fiber is completely covered, and the uniform penetration inside the fiber entangled body is obtained, which is advantageous for uniform impregnation. It is preferable in that it is uniform and does not impair the texture of the resulting artificial leather.
本発明の繊維絡合体としては、公知の方法を用いることができる。例えば、上記で得られる極細繊維発生型繊維を捲縮付与した後ステープル化し、カード、クロスラッパー、ランダムウエバー等によりウエブを形成し、ニードルパンチにより繊維を絡ませ、必要に応じ乾熱収縮、熱水収縮、熱プレスすることで得られる。得られた繊維絡合体は人工皮革として仕上げ、その用途によって任意に選択でき特に制限されるものではないが、目付は６００〜１５００ｇ/ｍ２、密度０．２０〜０．８０ｇ/ｃｍ３が好ましく、０．２５〜０．７０ｇ/ｃｍ３がより好ましい。０．２０ｇ/ｃｍ３未満では立毛調人工皮革としたときの繊維の立毛感や人工皮革基体の機械物性が不足し、０．８０ｇ/ｃｍ３を越えると人工皮革基体の風合いが硬くなってしまう。そして繊維絡合体の厚みは該目付け範囲および密度範囲を満たしていれば特に限定されないが、厚み斑が大きい場合、供給する高分子弾性体水分散液が繊維絡合体供給面で付着斑を生じやすいため、厚み斑としては繊維絡合体平均厚みの±７．５％以下が好ましく、±５．０％以下がより好ましい。なおここでいう繊維絡合体平均厚みとは、繊維絡合体１０箇所以上の厚み測定を行ない、その値から算出した平均値を指す。 A known method can be used as the fiber entangled body of the present invention. For example, the ultrafine fiber-generating fiber obtained above is crimped and then stapled, a web is formed with a card, a cross wrapper, a random web, etc., the fibers are entangled with a needle punch, and if necessary, dry heat shrinkage, hot water It can be obtained by shrinking and hot pressing. The obtained fiber entangled body is finished as an artificial leather and can be arbitrarily selected according to its use and is not particularly limited, but the basis weight is preferably 600 to 1500 g / m 2 and a density of 0.20 to 0.80 g / cm 3. 0.25 to 0.70 g / cm 3 is more preferable. If it is less than 0.20 g / cm 3 , the feeling of napping of the fibers and the mechanical properties of the artificial leather base will be insufficient when the artificial leather base is used, and if it exceeds 0.80 g / cm 3 , the texture of the artificial leather base will be hard. . The thickness of the fiber entangled body is not particularly limited as long as the weight range and the density range are satisfied. However, when the thickness unevenness is large, the polymer elastic body aqueous dispersion to be supplied tends to cause adhesion spots on the fiber entangled body supply surface. Therefore, the thickness unevenness is preferably ± 7.5% or less, more preferably ± 5.0% or less of the average thickness of the fiber entanglement. In addition, the fiber entangled body average thickness here refers to the average value calculated from the thickness measured at 10 or more positions of the fiber entangled body.
前記した通り、水溶性高分子成分と水難溶性高分子成分からなる極細繊維発生型繊維で構成される繊維絡合体へ高分子弾性体水分散液を含浸する際、特に繊維絡合体の密度が高い場合、含浸圧力だけで浸透させるには含浸圧力を過剰に高めない限り、繊維絡合体内の厚さ方向に均一に含浸液が含浸しないうちに繊維絡合体が含浸処理を終了してしまい、充分に高分子弾性体水分散液を含浸させ難い。その対策として繊維絡合体の含浸側とは反対側から更に吸引を行うか、または含浸処理速度を低下させなければならず、複雑な設備が必要となり、また高分子弾性体水分散液の含浸に比較的長時間を要し、生産効率が低下する傾向がある。しかしながら無理に含浸圧力を高めた場合、繊維絡合体と含浸装置との境界面から含浸液の漏出が生じて適量の含浸が困難となる傾向がある。本発明は繊維絡合体に対する高分子弾性体水分散液の浸透性と含浸圧力を調整することで、煩雑なプロセスを用いること無く、また含浸圧力を高めること無く、繊維絡合体の内部に高分子弾性体水分散液を均一な状態でかつ短時間で含浸処理することを可能とするものである。まず高分子弾性体水分散液の浸透性に関しては、繊維絡合体への浸透時間を１０秒以下に調節した高分子弾性体水分散液を用いることが重要であり、５秒以下が好ましく、２秒以下がより好ましい。１０秒を越える場合、繊維絡合体へ供給された全ての高分子弾性体水分散液が繊維絡合体内部へ均一にかつ十分に含浸しきれず、高分子弾性体水分散液が繊維絡合体供給面から溢れ溶液供給部周辺を汚染し、更には繊維絡合体内部での含浸樹脂量が不足したものとなる。
なお、ここでいう浸透時間とは、高分子弾性体水分散液と繊維絡合体の相対的な浸透時間をいい、含浸する高分子弾性体水分散液０．０３５ｃｃを１０ｃｍの高さから繊維絡合体へ滴下し、滴下時より完全に浸透するまでの時間を測定したものである。また、完全に浸透するとは、高分子弾性体水分散液が繊維絡合体上に盛り上がった状態でなくなることを目視で確認できた状態をいう。そして、本発明の浸透時間となるように適宜高分子弾性体水分散液の粘度や濃度を調整した後に処理すれば良い。繊維絡合体の密度が０．２０〜０．８０ｇ／ｍ３の場合、高分子弾性体水分散液の粘度は２〜８０ｃｐｏｉｓｅが好ましく、濃度は３０〜６０％とする組み合せが浸透時間を１０秒以下としやすい点で好ましい。 また高分子弾性体水分散液濃度は、３５〜５０質量％であることがより好ましい。３０質量％未満では乾燥工程でマイグレーションを生じやすく、また６０質量％を越える場合、前記した浸透時間が増加傾向にあり、所定量の含浸樹脂量が低下する傾向がある。
また、繊維絡合体と高分子弾性体水分散液の粘度および濃度の組みわ合せが上記のままの組み合せでは浸透時間が１０秒を越える場合、浸透性向上のために高分子弾性体水分散液中へ界面活性剤を適宜添加して１０秒以下とすることが良い。界面活性剤としては、湿潤剤、浸透剤、レベリング剤など公知のものが使用でき、中でもスルホコハク酸ジー２−エチルヘキシルエステルナトリウム塩、スルホコハク酸ジオクチルエステルナトリウム塩、ドデシルベンゼンスルホン酸ナトリウム等のスルホン酸塩型アニオン界面活性剤：ラウリル硫酸エステルナトリウム、硫酸化オレイン酸ブチルエステルナトリウム塩、ジブチルナフタレンスルホン酸ナトリウム等の硫酸エステル塩型アニオン界面活性剤：ポリエチレングリコールーモノー４ーノニルフエニルエーテル、ポリエチレングリコールーモノーオクチルエーテル、ポリエチレングリコールーモノーデシルエーテル等のＨＬＢ価６〜１６のポリエチレングリコール型ノニオン界面活性剤：フッ素系界面活性剤、シリコン系界面活性剤から選ばれる１種以上を用いることが好ましい。
As described above, when a polymer elastic body aqueous dispersion is impregnated into a fiber entanglement composed of ultrafine fiber-generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component, the density of the fiber entanglement is particularly high. In the case of impregnation with only the impregnation pressure, unless the impregnation pressure is increased excessively, the fiber entangled body finishes the impregnation treatment before the impregnation liquid is uniformly impregnated in the thickness direction in the fiber entangled body, and is sufficient. It is difficult to impregnate with the polymer elastic water dispersion. As countermeasures, it is necessary to perform further suction from the side opposite to the impregnation side of the fiber entangled body, or to reduce the impregnation processing speed, which requires complicated equipment, and for impregnation with the polymer elastic water dispersion. It takes a relatively long time and tends to reduce production efficiency. However, when the impregnation pressure is forcibly increased, the impregnation liquid leaks from the interface between the fiber entangled body and the impregnation apparatus, and there is a tendency that an appropriate amount of impregnation becomes difficult. The present invention adjusts the permeability and impregnation pressure of the polymer elastomer aqueous dispersion with respect to the fiber entangled body, without using a complicated process and without increasing the impregnation pressure, the polymer inside the fiber entangled body. The elastic water dispersion can be impregnated in a uniform state in a short time. First, regarding the permeability of the polymer elastic water dispersion, it is important to use a polymer elastic water dispersion in which the penetration time into the fiber entanglement is adjusted to 10 seconds or less, preferably 5 seconds or less. More preferred is seconds or less. When the time exceeds 10 seconds, all of the polymer elastic water dispersion supplied to the fiber entangled body cannot be uniformly and sufficiently impregnated inside the fiber entangled body, and the polymer elastic water dispersion is not supplied to the fiber entangled body supply surface. Overflowing and contaminating the periphery of the solution supply section, and further, the amount of impregnating resin inside the fiber entangled body becomes insufficient.
The penetration time here refers to the relative penetration time of the polymer elastic water dispersion and the fiber entangled body, and 0.035 cc of the polymer elastic water dispersion to be impregnated from the height of 10 cm to the fiber entanglement. The time from dropping to the coalescence and complete penetration from the time of dropping is measured. Moreover, completely penetrating means a state in which it can be visually confirmed that the aqueous polymer elastic dispersion is no longer raised on the fiber entangled body. Then, the treatment may be carried out after appropriately adjusting the viscosity and concentration of the polymer elastomer aqueous dispersion so as to be the permeation time of the present invention. In the case where the density of the fiber entanglement is 0.20 to 0.80 g / m 3 , the viscosity of the polymer elastic body aqueous dispersion is preferably 2 to 80 cpoise, and the combination with the concentration of 30 to 60% has an infiltration time of 10 seconds. This is preferable because it can be easily made as follows. The concentration of the elastic polymer aqueous dispersion is more preferably 35 to 50% by mass. If it is less than 30% by mass, migration tends to occur in the drying step, and if it exceeds 60% by mass, the above-mentioned permeation time tends to increase, and the amount of the impregnated resin tends to decrease.
Also, when the combination of the viscosity and concentration of the fiber entangled body and the polymer elastic water dispersion is the same as described above, when the permeation time exceeds 10 seconds, the polymer elastic water dispersion is used to improve the permeability. It is preferable to add a surfactant to the inside to make it 10 seconds or less. As the surfactant, known ones such as a wetting agent, a penetrating agent, and a leveling agent can be used. Among them, sulfonic acid salts such as di-2-ethylhexyl sulfosuccinate sodium salt, dioctyl ester sulfosuccinate sodium salt, sodium dodecylbenzenesulfonate, etc. Type anionic surfactants: sulfated salt type anionic surfactants such as sodium lauryl sulfate, sodium butyl sulfate oleate, sodium dibutylnaphthalene sulfonate: polyethylene glycol-mono-4-nonyl phenyl ether, polyethylene glycol Polyethylene glycol type nonionic surfactants having an HLB value of 6 to 16, such as monooctyl ether and polyethylene glycol mono-decyl ether: fluorinated surfactant, silicon based surfactant It is preferred to use at least one member selected from.
本発明の高分子弾性体水分散液の含浸方法においては繊維絡合体に対する高分子弾性体水分散液の浸透性が前記の範囲を満足すると共に含浸圧力を調整する必要がある。特に繊維絡合体内部に高分子弾性体をより均一に含浸するためには繊維絡合体の密度や目付にもよるが、供給する高分子弾性体の含浸圧力は１，０００〜１００，０００Ｐａが必要であり、２０００〜８００００Ｐａが好ましく、２０００〜５００００Ｐａがより好ましい。１，０００Ｐａ未満では供給する高分子弾性体水分散液を、人工皮革基体の繊維絡合体に対し高分子弾性体供給面から反対側まで充分浸透ができず、さらには得られる人工皮革基体の風合いが低下する。一方１００，０００Ｐａを越える場合、浸透性は良好であるが供給される高分子弾性体が供給面から洩れを生じ、周囲が汚染され作業性が低下する。前記範囲の高分子弾性体水分散液の含浸圧力で含浸する繊維絡合体としては、高分子弾性体水分散液の浸透性が１０秒以下である繊維絡合体を用いることが必要であり、繊維絡合体の密度が０．２０〜０．８０ｇ/ｃｍ３、目付が６００〜１５００ｇ/ｍ２であることがより好ましい。なお、ここでいう高分子弾性体水分散液の含浸圧力とは、繊維絡合体へ接している液溜室内の圧力を指し、該液溜室へ液圧測定装置を設置しておくことで求めることができる。ここでの液圧測定装置は測定できるものであれば特に限定されない。 In the method of impregnating the polymer elastic water dispersion of the present invention, it is necessary that the permeability of the polymer elastic water dispersion with respect to the fiber entanglement satisfies the above range and the impregnation pressure is adjusted. In particular, in order to more uniformly impregnate the polymer elastic body into the fiber entangled body, depending on the density and basis weight of the fiber entangled body, the impregnation pressure of the supplied polymer elastic body needs 1,000 to 100,000 Pa. 2000 to 80000 Pa is preferable, and 2000 to 50000 Pa is more preferable. If it is less than 1,000 Pa, the polymer elastic water dispersion to be supplied cannot sufficiently permeate the fiber entangled body of the artificial leather substrate from the polymer elastic material supply surface to the opposite side, and further the texture of the artificial leather substrate to be obtained Decreases. On the other hand, when it exceeds 100,000 Pa, the permeability is good, but the supplied polymer elastic body leaks from the supply surface, the surroundings are contaminated, and the workability is lowered. As the fiber entanglement impregnated with the impregnation pressure of the polymer elastic water dispersion in the above range, it is necessary to use a fiber entanglement in which the permeability of the polymer elastic water dispersion is 10 seconds or less. It is more preferable that the density of the entangled body is 0.20 to 0.80 g / cm 3 and the basis weight is 600 to 1500 g / m 2 . The impregnation pressure of the polymer elastic water dispersion here refers to the pressure in the liquid storage chamber in contact with the fiber entanglement, and is obtained by installing a hydraulic pressure measuring device in the liquid storage chamber. be able to. The hydraulic pressure measuring device here is not particularly limited as long as it can measure.
本発明で繊維絡合体へ供給される高分子弾性体水分散液を構成する高分子弾性体としては、人工皮革に用いられる含浸用高分子弾性体であれば特に限定されないが、ウレタン系重合体、アクリル系重合体が好ましく用いられ、該重合体を水などの非溶剤中に分散させて得られる重合体分散液などが挙げられる。そして必要に応じて種々の有機系顔料および無機系顔料などを添加してもよく、その場合の有機顔料としては、例えばフタロシアニン系、アントラキノン系、キナクリドン系、ジオキサジン系、ぺリレン系、チオインジゴ系、アゾ系顔料等が挙げられ、また無機系顔料としては、酸化チタン、カーボンブラック、べんがら、クロムレッド、モリブデンレッド、リサージ、酸化鉄等が挙げられる。
また高分子弾性体水溶液を含浸した後、高分子弾性体を加熱凝固する。凝固する方法としては、公知の方法が挙げられるが、例えば、熱処理して乾式凝固、あるいは熱水処理、スチーム処理して感熱凝固する方法が好ましく挙げられる。
また本発明では、高分子弾性体水分散液に感熱ゲル化性化合物を添加する等の公知の方法で、繊維絡合体全体に均一に存在できるように高分子弾性体を凝固する方法を加えることがより好ましい。繊維絡合体全体に均一に存在できるように高分子弾性体を凝固する方法がより好ましい。
また粘度としては高分子弾性体水分散液の浸透性が阻害されない範囲であればよく、上記のように、２〜８０ｃｐｏｉｓｅが好ましく、５〜６０ｃｐｏｉｓｅがより好ましく、１０〜５０ｃｐｏｉｓｅが更に好ましい。
The polymer elastic body constituting the polymer elastic water dispersion supplied to the fiber entangled body in the present invention is not particularly limited as long as it is a polymer elastic body for impregnation used for artificial leather, but is a urethane polymer. An acrylic polymer is preferably used, and examples thereof include a polymer dispersion obtained by dispersing the polymer in a non-solvent such as water. If necessary, various organic pigments and inorganic pigments may be added. In this case, examples of the organic pigment include phthalocyanine, anthraquinone, quinacridone, dioxazine, perylene, thioindigo, Examples of the inorganic pigment include titanium oxide, carbon black, red pepper, chromium red, molybdenum red, resurge, and iron oxide.
Moreover, after impregnating the polymer elastic body aqueous solution, the polymer elastic body is heated and solidified. Examples of the solidification method include known methods. For example, a dry solidification by heat treatment or a method of heat-sensitive solidification by hot water treatment or steam treatment is preferable.
In the present invention, a method of coagulating the polymer elastic body is added by a known method such as adding a heat-sensitive gelling compound to the polymer elastic water dispersion so that it can be uniformly present throughout the fiber entangled body. Is more preferable. A method of solidifying the polymer elastic body so that it can exist uniformly throughout the fiber entangled body is more preferable.
The viscosity may be in a range that does not inhibit the permeability of the polymer elastic aqueous dispersion, and as described above, 2 to 80 cpoise is preferable, 5 to 60 cpoise is more preferable, and 10 to 50 cpoise is still more preferable.
そして繊維絡合体内部で均一な含浸を行なうために、高分子弾性体水分散液の供給量が繊維絡合体空隙量の６０〜１００％であることが重要であり、７０〜９９％が好ましい。なお、ここでいう繊維絡合体空隙量は、後述の計算方法によって求めることができる。高分子弾性体水分散液の供給量が繊維絡合体空隙量の６０％未満の場合、繊維絡合体の高分子弾性体分散液供給側とその反対側での含浸量が異なり、繊維絡合体内部での高分子弾性体分散液の分布が不均一となるため、該繊維絡合体からなる人工皮革基体を人工皮革に仕上げた場合、皮革様の風合いに劣り、さらに立毛調人工皮革に仕上げた場合の表面感が劣ったものとなる。一方、１００％を越える場合、繊維絡合体内部での高分子弾性体分散液の分布は均一であるが、供給過剰のため繊維絡合体の高分子弾性体分散液供給面と反対の面から該高分子弾性体水分散液が溢れ、接するローラーなどの含浸設備を汚染するのみならず繊維絡合体の不必要な部分にまで高分子弾性体水分散液が付着してしまい、工程通過性や作業性に問題を生じる。 In order to perform uniform impregnation inside the fiber entangled body, it is important that the supply amount of the polymer elastic body aqueous dispersion is 60 to 100% of the fiber entangled body void amount, and preferably 70 to 99%. In addition, the fiber entangled body void amount mentioned here can be obtained by a calculation method described later. When the supply amount of the polymer elastic body aqueous dispersion is less than 60% of the fiber entangled body void amount, the amount of impregnation on the polymer elastic body dispersion supply side and the opposite side of the fiber entangled body is different. When the artificial leather base made of the fiber entangled body is finished into artificial leather, the texture of the leather is inferior, and when it is finished into napped-toned artificial leather The surface feeling is inferior. On the other hand, when it exceeds 100%, the distribution of the polymer elastic dispersion within the fiber entangled body is uniform, but due to excessive supply, the surface of the fiber entangled body from the surface opposite to the polymer elastic dispersion liquid supply surface The polymer elastic water dispersion overflows and not only contaminates impregnation equipment such as the roller in contact with it, but also adheres to the unnecessary part of the fiber entanglement, so that the polymer elastic water dispersion can pass through the process and work. Cause problems with sex.
本発明で繊維絡合体へ高分子弾性体水分散液を供給する場合の含浸装置は、繊維絡合体の内部に加圧浸透させることを利用した含浸方法を用いた装置である必要がある、例えば繊維絡合体を走行させるバックロール、および該バックロールに近接して含浸具を配し、さらに該含浸具から高分子弾性体水分散液を供給するためのポンプを設けた装置であることが好ましい（例えば、図１を参照。）。そして、この場合のポンプは、単位時間当たりの液供給量が一定であり、含浸の条件に応じてその供給量の設定値を変更できるものであることがより好ましい。 In the present invention, the impregnation apparatus in the case of supplying the polymer elastomer aqueous dispersion to the fiber entangled body needs to be an apparatus using an impregnation method using pressure infiltration inside the fiber entangled body, for example, It is preferable that the apparatus is provided with a back roll for running the fiber entangled body, an impregnation tool arranged in the vicinity of the back roll, and a pump for supplying the polymer elastic body aqueous dispersion from the impregnation tool. (See, for example, FIG. 1). The pump in this case has a constant liquid supply amount per unit time, and it is more preferable that the set value of the supply amount can be changed according to the impregnation conditions.
含浸装置には、繊維絡合体が含浸具を通過する際の入口と出口にエッジを設け、さらに処理方向と垂直の方向すなわち繊維絡合体横断方向（巾方向）両側に側壁を設け、該エッジと該側壁で囲まれた液溜め室が形成されており、該液溜め室内のスリット状吐出口からポンプにより定量の高分子弾性体水分散液を繊維絡合体の内部に加圧浸透させて供給する。側壁は液溜め室の液体をシールできれば特に限定されないが、供給される高分子弾性体水分散液が繊維絡合体の両端から洩れることなく全て繊維絡合体内部へ浸透させるため、繊維絡合体横断方向両側に設けている側壁の間隔（高分子弾性体水分散液供給幅）は繊維絡合体幅よりも狭めておくことが好ましく、各側壁は各繊維絡合体サイドより５ｃｍ以上内側であることがより好ましい。
そして該含浸装置は繊維絡合体の上方、あるいは下方、あるいは上下両方に設ける場合のいずれでもかまわないが、作業性およびコスト面から下方へ一箇所設置してあることが工業的に有利である。
In the impregnation apparatus, edges are provided at the inlet and outlet when the fiber entanglement passes through the impregnation tool, and side walls are provided on both sides in the direction perpendicular to the processing direction, that is, in the transverse direction (width direction) of the fiber entanglement. are liquid reservoir chamber surrounded by side wall is formed, supplying the elastic polymer aqueous dispersion of quantitatively is internally pressurized penetration of fiber-entangled body by liquid sump pump from the slit-shaped discharge port of the indoor . The side wall is not particularly limited as long as the liquid in the liquid storage chamber can be sealed, but the supplied polymer elastic water dispersion liquid penetrates into the fiber entangled body without leaking from both ends of the fiber entangled body. It is preferable that the interval between the side walls provided on both sides (polymer elastic body aqueous dispersion supply width) is narrower than the fiber entangled width, and each side wall is more than 5 cm inside from each fiber entangled side. preferable.
The impregnation apparatus may be provided above, below, or both above and below the fiber entangled body, but it is industrially advantageous to be installed at one place from the viewpoint of workability and cost.
そして本発明の高分子弾性体水分散液の含浸方法は、繊維絡合体が含浸直前に繊維絡合体厚みの４０〜９９％の間隙で圧縮される必要があり、７０〜９８％であることが好ましい。繊維絡合体厚みの４０％よりも強く圧縮されている場合、繊維絡合体と含浸装置の摩擦抵抗が大きく繊維絡合体の走行を阻害し、所定の速度で繊維絡合体が走行できないことから、繊維絡合体長さ方向における均一で安定な含浸が困難になる。また繊維絡合体厚みの９９％を越える弱い圧縮では、繊維絡合体への高分子弾性体水分散液供給面から液が洩れやすく、含浸具周囲が汚染されてしまい、また所定量供給された高分子弾性体水分散液が全て浸透できないことから高分子弾性体含浸量が計算による使用予定量より不足してしまう傾向がある。従って圧縮の間隙は広すぎても、狭すぎても均一で安定な含浸が困難な結果となる。なお含浸後に繊維絡合体を圧縮する場合、水溶性高分子が溶出することで高分子弾性体水分散液を汚染し、また極細繊維発生型繊維を構成する水溶性高分子成分が過剰に溶出すると水難溶性高分子成分が直接露出し易い傾向にあり、高分子弾性体水分散液中の高分子弾性体が極細繊維を直接把持し、得られる人工皮革の風合いが硬く劣ったものとなることから、含浸直前に繊維絡合体を圧縮し圧縮された状態にて含浸することが必要である。なお、供給された高分子弾性体水分散液が繊維絡合体内部へ浸透し所定量含浸したものに加え繊維絡合体供給面に過剰に付着することで表面層を形成してしまう場合には、繊維絡合体の出口にエッジを設けることによって、該表面層を除去することも可能である。 In the method of impregnating the polymer elastic water dispersion of the present invention, the fiber entangled body needs to be compressed at a gap of 40 to 99% of the fiber entangled body thickness just before the impregnation, and is 70 to 98%. preferable. When compressed more than 40% of the fiber entangled body thickness, the fiber entangled body and the impregnation device have a large frictional resistance, which inhibits the fiber entangled body from running and the fiber entangled body cannot run at a predetermined speed. Uniform and stable impregnation in the entangled body length direction becomes difficult. In addition, when the compression is weaker than 99% of the fiber entanglement thickness, the liquid is easily leaked from the supply surface of the polymer elastic body water dispersion to the fiber entanglement, and the periphery of the impregnating tool is contaminated. Since all of the molecular elastic body aqueous dispersion cannot penetrate, the polymer elastic body impregnation amount tends to be deficient from the estimated use amount by calculation. Accordingly, if the compression gap is too wide or too narrow, uniform and stable impregnation is difficult. When compressing the fiber entangled body after impregnation, if the water-soluble polymer is eluted, the polymer elastic body aqueous dispersion is contaminated, and if the water-soluble polymer component constituting the ultrafine fiber generating fiber is excessively eluted. Since the poorly water-soluble polymer component tends to be directly exposed, the polymer elastic body in the polymer elastic water dispersion directly grips the ultrafine fibers, and the resulting artificial leather has a hard and inferior texture. It is necessary to impregnate the fiber entangled body in a compressed state immediately before impregnation. In addition, in the case where the surface layer is formed by excessively adhering to the fiber entangled body supply surface in addition to the polymer entangled body aqueous dispersion that has penetrated into the fiber entangled body and impregnated with a predetermined amount, It is also possible to remove the surface layer by providing an edge at the exit of the fiber entangled body.
また該含浸装置を用いて含浸する場合は、高分子弾性体水分散液が浸透する時間を確保できれば生産速度を低下させなくとも処理が可能である。好ましくは２ｍ／ｍｉｎ以上であり、より好ましくは２〜１０ｍ／ｍｉｎであればよい。２ｍ／ｍｉｎ未満では高分子弾性体水分散液の浸透は充分可能であるが、処理速度が遅いことから生産性が低下してしまい、また１０ｍ／ｍｉｎを越える場合、浸透時間によっては供給された高分子弾性体水分散液を全て浸透しきれない場合が生じ、所定量の含浸が困難な場合を生じる懸念がある。また、含浸は可能であっても凝固乾燥が不十分となる懸念があり、これらが払拭されれば１０ｍ／分以上での処理も可能である。 In the case of impregnation using the impregnation apparatus, the treatment can be performed without reducing the production rate if the time for the polymer elastic water dispersion to permeate can be secured. Preferably it is 2 m / min or more, More preferably, it should just be 2-10 m / min. If it is less than 2 m / min, penetration of the polymer elastic water dispersion is sufficiently possible, but the productivity is lowered due to slow processing speed, and if it exceeds 10 m / min, it is supplied depending on the penetration time. There may be a case where the entire polymer elastic body aqueous dispersion cannot be completely penetrated, and there is a concern that a predetermined amount of impregnation is difficult. Moreover, even if impregnation is possible, there is a concern that coagulation and drying will be insufficient, and if these are wiped away, treatment at 10 m / min or more is possible.
また含浸される高分子弾性体水分散液は、高分子弾性体：極細繊維絡合体＝１５：８５〜６０：４０の質量比となるように付与することが好ましい。人工皮革として仕上げる場合、高分子弾性体は繊維を結束するバインダーとしての効果を得るものであり、１５質量％未満の場合、バインダー効果を充分満足できず、また６０質量％を越える場合、前述した効果が得られるものの、引裂強力、引張強力などの物性が劣り、また風合いが固く劣ったものとなる。
本発明の高分子弾性体水分散液を含浸する方法は、浸透性と含浸圧力等を調整することで高分子弾性体水分散液供給量全てを繊維絡合体へ所定量、かつ均一に含浸できることから、ニップロールを使わなくとも、高分子弾性体：極細繊維絡合体＝１５：８５〜６０：３５の質量比調整を高分子弾性体水分散液の供給量と濃度調整だけで行なえる。ニップロール処理が不要となることで、さらに繊維絡合体表面が有する水溶性高分子を高分子弾性体水分散液に溶出することを防ぐことができ、またシワ、伸びの発生などの問題も解消することができる。
Moreover, it is preferable to provide the polymer elastic body aqueous dispersion to be impregnated so that the mass ratio of polymer elastic body: extra fine fiber entangled body = 15: 85-60: 40. When finished as artificial leather, the polymer elastic body has an effect as a binder for binding fibers. When the amount is less than 15% by mass, the binder effect cannot be sufficiently satisfied. Although the effect is obtained, the physical properties such as tear strength and tensile strength are inferior, and the texture is hard and inferior.
The method of impregnating the polymer elastic water dispersion of the present invention is capable of uniformly impregnating the fiber entangled body with a predetermined amount and all of the polymer elastic water dispersion supply amount by adjusting the permeability and the impregnation pressure. Therefore, without using a nip roll, the mass ratio of polymer elastic body: extra fine fiber entanglement = 15: 85 to 60:35 can be adjusted only by adjusting the supply amount and concentration of the polymer elastic body aqueous dispersion. By eliminating the need for nip roll treatment, it is possible to further prevent the water-soluble polymer on the surface of the fiber entangled body from eluting into the water dispersion of the polymer elastic body, and to solve problems such as wrinkles and elongation. be able to.
極細繊維発生型繊維からなる繊維絡合体へ高分子弾性体水分散液を含浸した後、極細繊維および高分子弾性体の非溶剤であり且つ抽出除去成分の溶剤である処理液で抽出除去成分を除去し、極細繊維発生型繊維を極細化する。
特に抽出除去する場合、環境問題の点から熱水、アルカリ液などの水系溶媒で抽出除去成分を除去して極細繊維発生型繊維を極細化する方法が好ましい。特に熱水抽出する場合は、熱水温度として６０〜１００℃の温度が好ましく、８０〜９５℃がより好ましい。６０℃未満では水溶性高分子の除去に時間を要することから熱水温度は高いほど好ましい。しかし１００℃を越える温度を付与した際、樹脂と繊維の結束がゆるみ易く、樹脂が有する繊維把持性の低下が懸念されるため１００℃以下の範囲が好ましい。また必要に応じて所望の厚みに加圧加熱処理や分割処理などで厚みあわせを行う。また、極細繊維発生型繊維を極細化する前あるいは後に、少なくとも一面をバフィング処理等の起毛処理を施し、極細繊維を主体とした極細繊維立毛面を形成させて立毛調人工皮革としてもよい。またその場合、必要により、揉み柔軟化処理、逆シールのブラッシングなどの仕上げ処理を行うことができる。
After impregnating the fiber entanglement made of ultrafine fiber-generating fibers with an aqueous dispersion of a polymer elastic body, the extraction / removal component is treated with a treatment liquid which is a non-solvent for the ultrafine fiber and the polymer elastic body and is a solvent of the extraction / removal component. Remove and refine the ultrafine fiber generating fiber.
In particular, in the case of extraction and removal, from the viewpoint of environmental problems, a method in which the extraction and removal component is removed with an aqueous solvent such as hot water or an alkaline solution to make the ultrafine fiber generating fiber ultrafine is preferable. When extracting with hot water especially, the temperature of 60-100 degreeC is preferable as hot water temperature, and 80-95 degreeC is more preferable. When the temperature is lower than 60 ° C., it takes time to remove the water-soluble polymer, so that the hot water temperature is preferably higher. However, when a temperature exceeding 100 ° C. is applied, the binding between the resin and the fiber is easy to loosen, and there is a concern that the fiber gripping property of the resin may be lowered. If necessary, the thickness is adjusted to a desired thickness by pressure heating treatment or division treatment. In addition, before or after the ultrafine fiber-generating fiber is made ultrafine, at least one surface may be subjected to raising treatment such as buffing to form an ultrafine fiber raised surface mainly composed of ultrafine fibers to form a napped artificial leather. In that case, finishing treatment such as stagnation softening and reverse seal brushing can be performed as necessary.
本発明の人工皮革は、必要に応じて樹脂層を付与して、銀付き調あるいは半銀付き調の人工皮革とすることもできる。また、表面を加熱し、平滑面に押圧することにより不織布表層部を溶融して樹脂層とすることもできる。表面に付与する樹脂としては、ポリウレタンやアクリルで代表される弾性重合体が好適に用いられる。また、極少量の染料あるいは少量の顔料を用いて着色処理を行っても良い。また、必要に応じて、本発明の人工皮革を上層に使用し、編物あるいは編物を下層となるよう貼り合わせたり、あるいは、本発明の立毛調人工皮革を上層に使用し、該立毛調人工皮革を構成する繊維とは異種の繊維からなる層を下層となるよう貼り合わせたりしても構わない。 The artificial leather of the present invention can be provided with a resin layer as necessary to obtain an artificial leather with a tone with silver or with a semi-silver. Moreover, the nonwoven fabric surface layer part can be melted to form a resin layer by heating the surface and pressing it on a smooth surface. As the resin applied to the surface, an elastic polymer typified by polyurethane or acrylic is preferably used. Further, the coloring treatment may be performed using a very small amount of dye or a small amount of pigment. Further, if necessary, the artificial leather of the present invention is used as an upper layer, and a knitted fabric or a knitted fabric is bonded together as a lower layer, or the raised nail artificial leather of the present invention is used as an upper layer, and the napped-toned artificial leather A layer made of a different kind of fiber from the fibers constituting the layer may be bonded to form a lower layer.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。なお以下の実施例、比較例中に記載されている性能測定などの評価は以下の方法で行なった。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. In addition, evaluation, such as the performance measurement described in the following examples and comparative examples, was performed by the following method.
[浸透時間測定]
高分子弾性体水分散液として、グレー水分散顔料(大日本インキ化学工業株式会社製 ＲｙｕｄｙｅＷグレー)とエーテル系ポリウレタン水分散エマルジョン (第一工業製薬株式会社製 スーパーフレックス Ｅ−４８００)を顔料／エマルジョン＝１．８/１００の固形分質量比に混合し、濃度４０質量％、粘度１０ｃｐｏｉｓｅ、密度１．０２ｇ／ｃｍ３の高分子弾性体水分散液を作成し、該高分子弾性体水分散液０．０３５ｃｃを１０ｃｍの高さから繊維絡合体へ滴下し、滴下時より完全に浸透するまでの時間を測定した。
[Measurement of penetration time]
Gray water dispersion pigment (Ryudye W Gray, manufactured by Dainippon Ink & Chemicals, Inc.) and ether polyurethane water dispersion emulsion (Superflex E-4800, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as pigment / emulsion = Mixed solid mass ratio of 1.8 / 100 to prepare a polymer elastic water dispersion having a concentration of 40% by weight, a viscosity of 10 cpoise and a density of 1.02 g / cm 3 , and the polymer elastic water dispersion 0.035 cc was dropped onto the fiber entangled body from a height of 10 cm, and the time until completely penetrating from the time of dropping was measured.
[繊維絡合体空隙量]
単位時間あたりに処理する繊維絡合体空隙量は以下の計算式より算出した。
Ａ＝ＤＥＦＧ×（Ｃ／Ｄ−１）／Ｂ
Ａ（ｃｍ3／ｍｉｎ） ： 繊維絡合体空隙量
Ｂ（ｇ／ｃｍ3） ： 高分子弾性体水分散液の密度
Ｃ（ｇ／ｃｍ3） ： 繊維構成樹脂の密度
Ｄ（ｇ／ｃｍ3） ： 繊維絡合体の見掛け密度
Ｅ（ｃｍ） ： 繊維絡合体の厚み
Ｆ（ｃｍ） ： 高分子弾性体水分散液塗布幅
Ｇ（ｃｍ／ｍｉｎ） ： 走行速度
[Fiber entangled void volume]
The fiber entangled void amount to be treated per unit time was calculated from the following calculation formula.
A = DEFG × (C / D−1) / B
A (cm 3 / min): Fiber entanglement void volume B (g / cm 3 ): Density C (g / cm 3 ) of polymer elastic body aqueous dispersion: Density D (g / cm 3 ) of fiber constituent resin : Apparent density E (cm) of fiber entangled body: Thickness F (cm) of fiber entangled body: Application width G (cm / min) of polymer elastic body aqueous dispersion: Traveling speed
イソフタル酸１０モル％共重合ポリエチレンテレフタレート（融点２３４℃）を島成分とし、エチレン単位１０モル％含有し、けん化度９８．４モル％、融点２１０℃のポリビニルアルコール共重合体(株式会社クラレ製 エクセバール)を海成分とし、質量比を海/島＝３０/７０とした６４島の繊維を複合紡糸した後、延伸することで繊度５．５デシテックス、島成分繊度０．０６デシテックス、繊維構成樹脂密度１．２７ｇ／ｃｍ３の繊維を得た。この繊維を捲縮処理した後５１ｍｍへカットし、カード、ニードル処理し、１８５℃の乾熱収縮により２０％面積収縮し、１７０℃熱プレスすることで目付け１０８０ｇ/ｃｍ２、見掛け密度０．６４ｇ／ｃｍ３、平均厚み１．６８ｍｍ、厚み斑±４．５％の繊維絡合体を得た。 Polyvinyl alcohol copolymer (Exeval made by Kuraray Co., Ltd.) containing 10 mol% of isophthalic acid copolymerized polyethylene terephthalate (melting point: 234 ° C), containing 10 mol% of ethylene units, a saponification degree of 98.4 mol%, and a melting point of 210 ° C ) Is a sea component, and 64 island fibers having a mass ratio of sea / island = 30/70 are composite-spun, and then drawn to obtain a fineness of 5.5 dtex, an island component fineness of 0.06 dtex, and a fiber constituent resin density 1.27 g / cm 3 of fiber was obtained. This fiber is crimped, cut to 51 mm, processed with a card and a needle, subjected to a 20% area shrinkage by dry heat shrinkage at 185 ° C., and heat-pressed at 170 ° C. to give a basis weight of 1080 g / cm 2 and an apparent density of 0.64 g. / Cm 3 , an average thickness of 1.68 mm, and a thickness entanglement of ± 4.5% was obtained.
次にグレー水分散顔料(大日本インキ化学工業株式会社製 ＲｙｕｄｙｅＷグレー)とエーテル系ポリウレタン水分散エマルジョン (第一工業製薬株式会社製 スーパーフレックス Ｅ−４８００)を顔料／エマルジョン＝１．８/１００の固形分質量比に混合し、濃度４０質量％、粘度１０ｃｐｏｉｓｅ、密度１．０２ｇ／ｃｍ３である高分子弾性体水分散液を得た。該高分子弾性体水分散液の前記した繊維絡合体への浸透時間は０．３７秒であった。 Next, a gray water-dispersed pigment (Ryudye W gray manufactured by Dainippon Ink & Chemicals, Inc.) and an ether-based polyurethane water-dispersed emulsion (Superflex E-4800 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) of pigment / emulsion = 1.8 / 100 The mixture was mixed in the solid content mass ratio to obtain an aqueous polymer elastic body dispersion having a concentration of 40% by mass, a viscosity of 10 cpoise, and a density of 1.02 g / cm 3 . The permeation time of the polymer elastic water dispersion into the fiber entangled body was 0.37 seconds.
次に含浸設備としてリップコーター設備（株式会社ヒラノテクシード製 リップダイレクト方式）を用い、バックローラー下部に設置されているノズルヘッド通過時の含浸直前の繊維絡合体圧縮を繊維絡合体に対して８６％の間隙で設定し、バックローラーを介して幅１００ｃｍの上記不織布を２．５ｍ／ｍｉｎで走行させた。このクリアランス設定で繊維絡合体は問題なく走行した。
塗布幅を９０ｃｍ設定となるように側壁を設け、該繊維絡合体へ前記した高分子弾性体水分散液を塗布、含浸する場合、繊維絡合体空隙量は２３２２ｃｍ３／ｍｉｎであった。ここで極細繊維化された繊維絡合体／高分子弾性体＝７０／３０の質量比となるよう、４０質量％の高分子弾性体水分散液を繊維絡合体空隙量の８４％に相当する１９５０ｃｃ／ｍｉｎ、また含浸圧力２００００Ｐａで供給した。その際、供給した高分子弾性体水分散液は、ノズルヘッドと繊維絡合体の隙間から洩れることなく、全て繊維絡合体中へ浸透していた。また高分子弾性体水分散液供給面では液切れ状態が均一なものが得られ、もう一方の面と同等の外観が得られていた。高分子弾性体水分散液含浸後、１６０℃の熱風乾燥機で３分３０秒間加熱凝固乾燥した。
Next, lip coater equipment (Hipano Techseed's lip direct method) is used as the impregnation equipment, and the fiber entanglement compression immediately before impregnation when passing through the nozzle head installed under the back roller is 86% of the fiber entanglement. The gap was set, and the nonwoven fabric having a width of 100 cm was run at 2.5 m / min through a back roller. With this clearance setting, the fiber entangled body traveled without problems.
When the side wall was provided so that the coating width was set to 90 cm, and the above-mentioned polymer elastic body aqueous dispersion was applied to and impregnated into the fiber entanglement, the fiber entanglement void amount was 2322 cm 3 / min. Here, 1950 cc corresponding to 84% of the amount of voids of the fiber entanglement is obtained by adding 40% by mass of the polymer elastic body aqueous dispersion so that the mass ratio of the fiber entangled body / polymer elastic body = 70/30 which is made into ultrafine fibers is obtained. / Min and at an impregnation pressure of 20000 Pa. At that time, all of the supplied polymer elastic water dispersion had permeated into the fiber entangled body without leaking from the gap between the nozzle head and the fiber entangled body. In addition, the polymer elastic water dispersion supply surface had a uniform liquid running state, and the same appearance as the other surface was obtained. After impregnation with the polymer elastic body aqueous dispersion, the mixture was heat-coagulated and dried for 3 minutes and 30 seconds with a hot air dryer at 160 ° C.
含浸後、両サイド５ｃｍの未含浸個所をカットし、９０℃の熱水でポリビニルアルコール共重合体成分を抽出することで人工皮革基体を得た。得られた人工皮革基体はシワ、伸びの発生が無く良好な外観であり、皮革様の均一な風合いや優れた物性を有する人工皮革基体であった。また高分子弾性体割合は、３１質量％であった。また、得られた人工皮革基体を２分割にスライスし、各々の高分子弾性体分布を調査した結果、高分子弾性体水分散液供給面側での高分子弾性体割合は３２質量％、もう片側の高分子弾性体割合は３０質量％であり、基体中の高分子弾性体水分散液分布はほぼ均一であった。 After impregnation, an unimpregnated portion of 5 cm on both sides was cut, and a polyvinyl alcohol copolymer component was extracted with hot water at 90 ° C. to obtain an artificial leather base. The obtained artificial leather substrate was an artificial leather substrate having a good appearance without wrinkles and elongation, and having a uniform leather-like texture and excellent physical properties. Moreover, the polymer elastic body ratio was 31 mass%. In addition, as a result of slicing the obtained artificial leather substrate into two parts and investigating the distribution of each polymer elastic body, the ratio of the polymer elastic body on the polymer elastic body aqueous dispersion supply surface side was 32% by mass. The proportion of the elastic polymer on one side was 30% by mass, and the distribution of the aqueous dispersion of the elastic polymer in the substrate was almost uniform.
実施例１の繊維絡合体厚み斑として±３％のものを使用する以外は実施例１と同様の操作を行なった。その結果、得られた人工皮革はシワ、伸びの発生がなく良好な外観であり、皮革様の均一な風合いや優れた物性を有する人工皮革基体であった。また、高分子弾性体割合は３１質量％とほぼ目標通りであった。同様に高分子弾性体分布は、高分子弾性体水分散液供給面側／反対側＝３２質量％／質量％３０とほぼ均一であった。 The same operation as in Example 1 was carried out except that a fiber entangled thickness variation of Example 1 of ± 3% was used. As a result, the obtained artificial leather was an artificial leather base having a good appearance without wrinkles and elongation, a uniform texture like leather, and excellent physical properties. The proportion of the elastic polymer was 31% by mass, which was almost as targeted. Similarly, the polymer elastic body distribution was substantially uniform with the polymer elastic water dispersion supply surface side / opposite side = 32% by mass / 30% by mass.
実施例１の繊維絡合体として見掛け密度０．５８ｇ／ｃｍ３、目付１２４６ｇ／ｃｍ２、平均厚み２．１ｍｍ、厚み斑±４．５％、実施例１で用いた高分子弾性体水分散液の濃度３５質量％を用い、高分子弾性体水分散液の繊維絡合体への浸透時間を０．２１秒とした。そして、繊維絡合体空隙量は３２３８ｃｍ３／ｍｉｎであるため、極細繊維化された繊維絡合体／高分子弾性体＝６５／３５の質量比となるよう、高分子弾性体水分散液を繊維絡合体空隙量の７４％に相当する２４００ｃｍ３／ｍｉｎで供給した。その他は実施例１と同様の操作を行った。その結果、得られた人工皮革はシワ、伸びの発生がなく良好な外観であり、皮革様の均一な風合いや優れた物性を有する人工皮革基体であった。また、高分子弾性体割合は３３質量％とほぼ目標通りであった。同様に高分子弾性体分布は、高分子弾性体水分散液供給面側／反対側＝３３質量％／３５質量％とほぼ均一であった。 The fiber entangled body of Example 1 has an apparent density of 0.58 g / cm 3 , a basis weight of 1246 g / cm 2 , an average thickness of 2.1 mm, a thickness variation of ± 4.5%, and the polymer elastic water dispersion used in Example 1 A concentration of 35% by mass was used, and the permeation time of the polymer elastic water dispersion into the fiber entangled body was 0.21 seconds. And since the fiber entangled body void volume is 3238 cm 3 / min, the polymer elastic body aqueous dispersion is mixed with the fiber entangle so that the mass ratio of ultra-fine fiber entangled body / polymer elastic body = 65/35 is obtained. It was supplied at 2400 cm 3 / min corresponding to 74% of the combined void amount. The other operations were the same as in Example 1. As a result, the obtained artificial leather was an artificial leather base having a good appearance without wrinkles and elongation, a uniform texture like leather, and excellent physical properties. The proportion of the elastic polymer was 33% by mass, which was almost as intended. Similarly, the polymer elastic body distribution was substantially uniform with the polymer elastic water dispersion supply surface side / opposite side = 33% by mass / 35% by mass.
実施例１の高分子弾性体水分散液供給時の含浸圧力を５００００Ｐａとする以外は実施例１と同様の操作を行なった。その結果、供給した高分子弾性体水分散液はノズルヘッドと繊維絡合体の隙間から洩れることなく、全て繊維絡合体中へ浸透していた。また得られた人工皮革はシワ、伸びの発生が無く良好な外観であり、皮革様の均一な風合いや優れた物性を有する人工皮革基体であった。また、高分子弾性体割合は、３１質量％であった。同様に高分子弾性体分布を調査した結果、高分子弾性体水分散液供給面側での高分子弾性体割合は３２質量％、もう片側の高分子弾性体割合は３０質量％であり、基体中の高分子弾性体分布はほぼ均一であった。 The same operation as in Example 1 was performed except that the impregnation pressure at the time of supplying the polymer elastic water dispersion of Example 1 was 50000 Pa. As a result, all of the supplied polymer elastic water dispersion penetrated into the fiber entangled body without leaking from the gap between the nozzle head and the fiber entangled body. Further, the obtained artificial leather was an artificial leather base having a good appearance without wrinkles and elongation and having a uniform leather-like texture and excellent physical properties. Moreover, the polymer elastic body ratio was 31 mass%. Similarly, as a result of examining the distribution of the polymer elastic body, the ratio of the polymer elastic body on the polymer elastic body aqueous dispersion supply surface side was 32% by mass, and the ratio of the polymer elastic body on the other side was 30% by mass. The distribution of the elastic polymer was almost uniform.
実施例１のノズルヘッド通過時の繊維絡合体圧縮率を繊維絡合体厚みの９０％設定とする以外は実施例１と同様の操作を行なった。その結果、得られた人工皮革基体はシワ、伸びの発生がなく良好な外観であり、皮革様の均一な風合いや優れた物性を有する人工皮革基体であった。また、高分子弾性体割合は３１質量％とほぼ目標通りであった。同様に高分子弾性体分布は、高分子弾性体水分散液供給面側／反対側＝３２質量％／３０質量％とほぼ均一であった。 The same operation as in Example 1 was performed except that the fiber entanglement compression rate when passing through the nozzle head of Example 1 was set to 90% of the fiber entanglement thickness. As a result, the obtained artificial leather substrate was an artificial leather substrate having a good appearance without wrinkles and elongation, and having a uniform leather-like texture and excellent physical properties. The proportion of the elastic polymer was 31% by mass, which was almost as targeted. Similarly, the polymer elastic body distribution was substantially uniform, ie, the polymer elastic water dispersion supply surface side / opposite side = 32 mass% / 30 mass%.
実施例１の高分子弾性体水分散液供給量を繊維絡合体空隙量の９７％である２２５０ｃｃ／ｍｉｎとし、繊維化された繊維絡合体／高分子弾性体＝６５／３５の質量比を目標として含浸処理する以外は実施例１と同様の操作を行なった。その結果、得られた人工皮革基体はシワ、伸びの発生がなく良好な外観であり、皮革様の均一な風合いや優れた物性を有する人工皮革基体であった。また、高分子弾性体割合は３４質量％とほぼ目標通りであった。同様に高分子弾性体分布は、高分子弾性体水分散液供給面側／反対側＝３５質量％／３４質量％とほぼ均一であった。
比較例１
The supply amount of the polymer elastomer aqueous dispersion in Example 1 is 2250 cc / min, which is 97% of the fiber entanglement void amount, and the mass ratio of fiber entangled polymer / polymer elastic body = 65/35 is targeted. The same operation as in Example 1 was performed except that the impregnation treatment was performed. As a result, the obtained artificial leather substrate was an artificial leather substrate having a good appearance without wrinkles and elongation, and having a uniform leather-like texture and excellent physical properties. The proportion of the elastic polymer was 34% by mass, which was almost as intended. Similarly, the polymer elastic body distribution was substantially uniform, ie, the polymer elastic water dispersion supply surface side / opposite side = 35 mass% / 34 mass%.
Comparative Example 1
実施例１の海成分としてポリエチレンを用い、また高分子弾性体溶液としてポリウレタンＤＭＦ溶液を用いる以外は実施例１と同様の操作を行なった。その結果、得られた人工皮革基体はシワ、伸びの発生はなかったが、繊維絡合体へのポリウレタンＤＭＦ溶液の浸透性が悪く、得られた基体の高分子弾性体割合は１５質量％と目標値に未達であり、高分子弾性体による極細繊維の結束が弱いため、機械物性に劣るものであり、表面平滑性に劣るものであった。
比較例２
The same operation as in Example 1 was carried out except that polyethylene was used as the sea component of Example 1 and a polyurethane DMF solution was used as the polymer elastic body solution. As a result, the obtained artificial leather substrate was not wrinkled or stretched, but the permeability of the polyurethane DMF solution to the fiber entangled body was poor, and the polymer elastic body ratio of the obtained substrate was 15% by mass. The value was not achieved, and the binding of ultrafine fibers by the polymer elastic body was weak, so that the mechanical properties were inferior and the surface smoothness was inferior.
Comparative Example 2
実施例１の繊維絡合体として見掛け密度０．９６ｇ／ｃｍ３、目付け１２４９ｇ/ｃｍ２、厚み１．３ｍｍ、厚み斑±４．５％を用い、高分子弾性体水分散液の繊維絡合体への浸透時間を２１秒とした。この繊維絡合体空隙量は８８１ｃｍ３／ｍｉｎであり、その９７％である８５５ｃｍ３／ｍｉｎで高分子弾性体水分散液を供給することで繊維化された繊維絡合体／高分子弾性体＝８５／１５の質量比を目標とし含浸処理を行う以外は実施例１と同様の操作を行なった。その結果、得られた人工皮革基体はシワ、伸びの発生はなかったが、繊維絡合体への高分子弾性体水分散液の浸透性が悪く、得られた人工皮革基体の高分子弾性体割合は８質量％と目標値に未達であった。
比較例３
Using the apparent density of 0.96 g / cm 3 , the basis weight of 1249 g / cm 2 , the thickness of 1.3 mm, and the thickness unevenness of ± 4.5% as the fiber entanglement of Example 1, to the fiber entanglement of the polymer elastic water dispersion The penetration time was 21 seconds. The fiber entangled body void amount is 881 cm 3 / min, and the fiber entangled body / polymer elastic body fiberized by supplying the polymer elastic body aqueous dispersion at 855 cm 3 / min, which is 97% = 85%. The same operation as in Example 1 was performed except that the impregnation treatment was performed with a target mass ratio of / 15. As a result, the obtained artificial leather base was not wrinkled or stretched, but the permeability of the polymer elastic body aqueous dispersion to the fiber entangled body was poor, and the ratio of the obtained polymer leather base to the polymer elastic body Was 8% by mass, not reaching the target value.
Comparative Example 3
実施例１の高分子弾性体水分散液供給時の含浸圧力を２０００００Ｐａとする以外は実施例１と同様の操作を行なった。その結果、高分子弾性体水分散液供給面から反対面まで高分子弾性体水分散液の浸透性は良好であるが、供給面から高分子弾性体水分散液の洩れが見られ、生産効率の低下のみならず、得られた人工皮革基体の外観に劣るものであった。
比較例４
The same operation as in Example 1 was performed except that the impregnation pressure at the time of supplying the polymer elastic water dispersion of Example 1 was set to 200000 Pa. As a result, the permeability of the polymer elastic water dispersion from the supply surface of the polymer elastic water dispersion to the opposite surface is good, but leakage of the polymer elastic water dispersion from the supply surface is seen, resulting in production efficiency. The appearance of the obtained artificial leather substrate was inferior as well as a decrease in the above.
Comparative Example 4
実施例１のノズルヘッド通過直前の圧縮率を繊維絡合体の間隙の３５％に設定とする以外は実施例１と同様の操作を行なった。その結果、ノズルヘッドと繊維絡合体間の摩擦抵抗が大きく、繊維絡合体の走行を阻害し、含浸処理が不可能であった。
比較例５
The same operation as in Example 1 was performed except that the compression ratio immediately before passing through the nozzle head of Example 1 was set to 35% of the gap of the fiber entangled body. As a result, the frictional resistance between the nozzle head and the fiber entangled body was large, obstructing the traveling of the fiber entangled body, and impregnation treatment was impossible.
Comparative Example 5
実施例１の高分子弾性体水分散液供給量を最大充填量の５５％である１２７８ｃｍ３／ｍｉｎ、高分子弾性体濃度を５８質量％とする以外は実施例１と同様の操作を行なった。その結果、得られた人工皮革基体はシワ、伸びの発生がなかったが、皮革様の均一な風合いおよび機械物性に劣るものであった。また、高分子弾性体分布は高分子弾性体水分散液供給面側／反対側＝４０質量％／２０質量％と不均一であった。
比較例６
The same operation as in Example 1 was performed, except that the polymer elastomer aqueous dispersion supply amount of Example 1 was 1278 cm 3 / min, which is 55% of the maximum filling amount, and the polymer elastomer concentration was 58% by mass. . As a result, the obtained artificial leather base was not wrinkled or stretched, but was inferior in leather-like uniform texture and mechanical properties. Further, the distribution of the polymer elastic body was nonuniform, ie, the polymer elastic water dispersion supply surface side / opposite side = 40 mass% / 20 mass%.
Comparative Example 6
実施例１の高分子弾性体水分散液供給方法としてディップニップ方式を用いた以外は実施例１と同様の操作を行った。その結果、高分子弾性体水分散液中に極細繊維発生型繊維を構成するポリビニルアルコール共重合体成分が溶出したため高分子弾性体水分散液粘度が増加し、含浸量を制御することが困難であった。また高分子弾性体水分散液含浸中にポリビニルアルコール共重合体成分が溶出していることから、得られた人工皮革基体は高分子弾性体が島成分の極細糸直接把持しており、風合いが固く、引き裂き強力に劣ったものであった。 The same operation as in Example 1 was performed except that the dip nip method was used as the polymer elastic water dispersion supply method of Example 1. As a result, since the polyvinyl alcohol copolymer component constituting the ultrafine fiber generating fiber was eluted in the polymer elastic water dispersion, the viscosity of the polymer elastic water dispersion increased and it was difficult to control the amount of impregnation. there were. In addition, since the polyvinyl alcohol copolymer component is eluted during the impregnation of the polymer elastic water dispersion, the resulting artificial leather substrate is directly gripped by the ultrathin yarn of the island elastic component of the polymer elastic body. It was hard and inferior in tearing strength.
１ バックローラー
２ ポンプ
３ リップコーター
４ 繊維絡合体
５ エマルジョン
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Claims (4)
（１）高分子弾性体水分散液をポンプを設けて加圧することにより、繊維絡合体の内部に該高分子弾性体水分散液を加圧浸透させることを利用した含浸方法であること
（２）繊維絡合体への浸透時間を１０秒以下に調節した高分子弾性体水分散液を用いること
（３）高分子弾性体水分散液の含浸圧力が１，０００〜１００，０００Ｐａであること
（４）繊維絡合体が含浸直前に繊維絡合体厚みの４０〜９９％の間隙で圧縮されていること
（５）高分子弾性体水分散液供給量が繊維絡合体空隙量の６０〜１００％であること When impregnating a polymer elastic body aqueous dispersion into a fiber entangled body composed of ultrafine fiber generating fibers composed of a water-soluble polymer component and a poorly water-soluble polymer component, the following (1) to (5) A method of impregnating an aqueous dispersion of a polymer elastic body, characterized by being satisfied.
(1) An impregnation method using pressurizing and penetrating the polymer elastic water dispersion into the fiber entangled body by pressurizing the polymer elastic water dispersion with a pump (2 ) Use a polymer elastic water dispersion whose penetration time into the fiber entangled body is adjusted to 10 seconds or less. (3) The impregnation pressure of the polymer elastic water dispersion is 1,000 to 100,000 Pa ( 4) The fiber entangled body is compressed in a gap of 40 to 99% of the fiber entangled body thickness immediately before impregnation. (5) The polymer elastic body aqueous dispersion supply amount is 60 to 100% of the fiber entangled body void amount. There is
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