JP2007138310A - Flame-retardant leather-like sheet and process for imparting flame retardancy to leather-like sheet - Google Patents
Flame-retardant leather-like sheet and process for imparting flame retardancy to leather-like sheet Download PDFInfo
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本発明は、難燃性皮革様シートおよび難燃加工方法に関する。より詳細には、柔軟な風合い、優れた表面タッチおよび外観の難燃性皮革様シートに関する。 The present invention relates to a flame retardant leather-like sheet and a flame retardant processing method. More particularly, it relates to a flame retardant leather-like sheet having a soft texture, excellent surface touch and appearance.
皮革様シートは、従来から、インテリア、衣類、靴、鞄、手袋、乗物用座席の上張材などの様々な用途に利用されている。そのうちでも、鉄道車両用座席、自動車用座席、航空機用座席、船舶用座席などの乗物用座席、あるいはクッションシート、ソファー、椅子などのインテリアの上張材といった分野では、柔軟な風合や審美な表面外観を有することはもちろんのこと各種堅牢度や耐久性、耐磨耗性のみならず、優れた難燃性を兼ね備えた素材、特にスエード調皮革様シート素材が強く求められている。 Leather-like sheets are conventionally used in various applications such as interiors, clothing, shoes, bags, gloves, and vehicular seats. Among them, in the fields such as railcar seats, automobile seats, aircraft seats, ship seats such as ship seats, and interior coverings such as cushion seats, sofas, chairs, etc. In addition to having a surface appearance, there is a strong demand for materials that have not only various fastnesses, durability, and abrasion resistance, but also excellent flame retardancy, particularly suede-like leather-like sheet materials.
従来、繊維質シートを基材とする皮革様シートに難燃性能を付与する方法としては、基材を構成する繊維自体にリン化合物などを含有させる方法や、塩素や臭素を主体としたハロゲン化合物やアンチモン化合物からなる難燃剤微粒子をバインダーによって基材の裏面側へ付着させる方法が一般的であり、特に極細繊維不織布を基材とする皮革様シートの場合には、繊維自体が細くて弱いため繊維強度を低下させる前者の方法ではなく、後者の方法が主流であった。しかしながら、毒性や焼却時の有害物質発生などの危険性が指摘され、世界的に使用が大幅制限される傾向にある方法である。
スエード調皮革様シートの難燃加工技術として、主に車両用シートや飛行機用シートとしての開発技術であるが、難燃剤をバックコートして行う方法が開示されている（例えば、特許文献１、特許文献２）しかしながら、得られるシートは風合いが硬化し、高級感に劣る傾向がある。また伸びが固定されるため、複雑な形をしたシート形状への追随ができ難い傾向がある。
Conventionally, as a method for imparting flame retardancy to a leather-like sheet based on a fiber sheet, a method of containing a phosphorus compound or the like in the fiber constituting the base material, or a halogen compound mainly composed of chlorine or bromine In general, in the case of a leather-like sheet based on an ultrafine fiber nonwoven fabric, the fiber itself is thin and weak. The latter method was the mainstream, not the former method for reducing fiber strength. However, there are dangers such as toxicity and generation of harmful substances at the time of incineration, and this method tends to be greatly restricted worldwide.
As a flame retardant processing technique for a suede leather-like sheet, it is a development technique mainly as a vehicle seat or an airplane seat, but a method of performing a back coating with a flame retardant is disclosed (for example, Patent Document 1, Patent Document 2) However, the obtained sheet has a hardened texture and tends to be inferior in a high-class feeling. Further, since the elongation is fixed, there is a tendency that it is difficult to follow a sheet shape having a complicated shape.
また、難燃剤を染色後の仕上げ工程で含浸付与する方法やポリウレタンに難燃剤を混合させる方法が開示されている（例えば、特許文献３参照。）しかしながら、これらの方法では難燃性能を発揮させるために難燃剤を多量に付着させる必要があり、表面のベタツキ感、風合いが低下する場合がある。さらに後者ではポリウレタン樹脂としての耐光性が低下傾向にあり、特に厳しい耐光性能が要求される車両用シートでは十分とはいえない。一般的にはポリウレタンに難燃剤などの添加剤を付与する方法では、難燃性能と樹脂性能の両立は困難な場合が多い。 In addition, a method of impregnating and imparting a flame retardant in a finishing step after dyeing and a method of mixing a flame retardant with polyurethane are disclosed (for example, see Patent Document 3). However, these methods exhibit flame retardancy. Therefore, it is necessary to attach a large amount of flame retardant, and the stickiness and texture of the surface may be lowered. Furthermore, in the latter, the light resistance as a polyurethane resin tends to decrease, and it cannot be said that a vehicle seat that requires particularly severe light resistance is sufficient. In general, in a method of adding an additive such as a flame retardant to polyurethane, it is often difficult to achieve both flame retardancy and resin performance.
また、リン系難燃剤を熱可塑性合成繊維に共重合させることにより、染色時の難燃剤の溶出や糸物性の劣化を克服した技術も開示されている（特許文献４参照。）しかしながら、コスト的な問題よりリン共重合繊維の割合に制約がかかり、高い難燃性とコストを両立し難いものであった。 In addition, a technology has been disclosed in which a phosphorus-based flame retardant is copolymerized with a thermoplastic synthetic fiber to overcome elution of the flame retardant during dyeing and deterioration of yarn physical properties (see Patent Document 4). Due to this problem, the proportion of the phosphorus copolymer fiber is restricted, and it is difficult to achieve both high flame retardancy and cost.
本発明の課題は、表面外観を損なうことがなく柔軟な風合いと優れた難燃性能をもつ皮革様シートおよびその加工方法を提供することである。 An object of the present invention is to provide a leather-like sheet having a flexible texture and excellent flame retardancy without impairing the surface appearance, and a processing method thereof.
本発明者らは、乗物用座席、クッションシート、ソファー、椅子などのインテリア製品の上張材などに好適に用いられる柔軟な風合いと難燃性能に優れた皮革様シートを得るにあたり鋭意検討した結果、本発明に至った。すなわち、本発明は、（１）気泡を含有させた状態で難燃剤液を皮革様シートの裏面に塗布することを特徴とする皮革様シートの難燃加工方法。
（２）難燃剤液中の難燃剤濃度が５〜６０質量％である（１）の皮革様シートの難燃加工方法。
（３）強制的に気泡を含有させた状態での難燃剤液の見掛け密度が０．１〜０．６ｇ／ｃｍ３となる状態で難燃剤を塗布する（１）または（２）の皮革様シートの難燃加工方法。
（４）難燃剤液が難燃剤の水分散液または水溶液からなる（１）〜（３）いずれかの難燃加工方法。
（５）皮革様シートの裏面側に難燃剤が塗布された難燃性皮革様シートにおいて、難燃剤液を、強制的に気泡を含有させた状態で皮革様シートの裏面に塗布し、該難燃剤を皮革様シート裏面から内部に渡って存在させ、かつ表面側には該難燃剤が存在していないことを特徴とする難燃性皮革様シート。
（６）皮革様シートが繊維絡合不織布に高分子弾性体を含浸したものであり、繊維絡合不織布と高分子弾性体との質量比が５０／５０〜９８／２である（５）の難燃性皮革様シート。
（７）皮革様シートが極細繊維絡合不織布からなるスエード調皮革様シートである（５）または（６）の難燃性皮革様シートである。
As a result of intensive studies on obtaining a leather-like seat excellent in a flexible texture and flame retardancy that is suitably used for an interior product such as a vehicle seat, cushion seat, sofa, chair, etc. The present invention has been reached. That is, the present invention provides (1) a flame-retardant processing method for a leather-like sheet, which comprises applying a flame retardant liquid to the back surface of the leather-like sheet in a state of containing bubbles.
(2) The flame retardant processing method for a leather-like sheet according to (1), wherein the flame retardant concentration in the flame retardant liquid is 5 to 60% by mass.
(3) The leather-like material of (1) or (2), in which the flame retardant is applied in a state where the apparent density of the flame retardant liquid in the state of forcibly containing bubbles is 0.1 to 0.6 g / cm 3 Flame-retardant processing method for sheets.
(4) The flame retardant processing method according to any one of (1) to (3), wherein the flame retardant liquid comprises an aqueous dispersion of a flame retardant or an aqueous solution.
(5) In a flame retardant leather-like sheet in which a flame retardant is applied to the back side of the leather-like sheet, the flame retardant liquid is forcibly applied to the back side of the leather-like sheet in a state of containing bubbles. A flame retardant leather-like sheet, wherein a flame retardant is present from the back side to the inside of the leather-like sheet, and the flame retardant is not present on the front side.
(6) The leather-like sheet is obtained by impregnating a fiber entangled nonwoven fabric with a polymer elastic body, and the mass ratio of the fiber entangled nonwoven fabric and the polymer elastic body is 50/50 to 98/2. Flame retardant leather-like sheet.
(7) The flame-retardant leather-like sheet according to (5) or (6), wherein the leather-like sheet is a suede-like leather-like sheet made of an ultrafine fiber-entangled nonwoven fabric.
本発明の難燃性皮革様シートは、表面外観を損なうことがなく柔軟な風合いと優れた難燃性能を有する。 The flame-retardant leather-like sheet of the present invention has a flexible texture and excellent flame retardancy without impairing the surface appearance.
本発明に用いられる皮革様シート様シートを構成する繊維は、特に制約は無いが、皮革様シートとした場合に皮革様の風合いが得られる点、さらにスエード調皮革様シートとした場合に優れた触感および細かなライティング効果が得られる点から、０．５ｄｔｅｘ以下の極細繊維であることが好ましい。その際、極細繊維は単成分を用いた直接紡糸から得られるもの、あるいは、少なくとも２種類のポリマーからなる極細繊維発生型繊維から作られる。上記の極細繊維発生型繊維は、例えば、海成分が溶剤または分解することで島成分がフィブリル化する抽出型繊維あるいは機械的にまたは処理剤によって各ポリマーからなる極細繊維にフィブリル化する分割型繊維等があげられる。極細繊維発生型繊維は、必要に応じて延伸、熱処理、機械捲縮、カット等の処理工程を経て繊度１〜１５ｄｔｅｘの短繊維、あるいは長繊維とする。極細繊維を構成するポリマーは、６−ナイロン、６６−ナイロン、１２−ナイロンなどの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、またはそれらの共重合体の溶融紡糸可能なポリエステル類から選ばれる少なくとも１種類のポリマーが用いられる。また、抽出型繊維で抽出または分解除去される成分は、極細繊維成分と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、極細繊維成分との相溶性の小さいポリマーであり、かつ紡糸条件下で極細繊維成分より溶融粘度が小さいかあるいは表面張力が小さいポリマーである必要がある。そして例えば、ポリエチレン、ポリスチレンまたはポリビニルアルコール等が用いられる。本発明においては環境汚染、溶解時の収縮特性等総合的に考慮すれば熱水で溶解可能なポリビニルアルコールを用いることがより好ましい。さらに、上記極細繊維は、本発明の効果を損なわない限りにおいてカーボンブラック等に代表される顔料で着色あるいは公知の繊維添加剤を添加することは可能である。 The fibers constituting the leather-like sheet-like sheet used in the present invention are not particularly limited, but the leather-like texture can be obtained when the leather-like sheet is used, and further excellent when the suede-like leather-like sheet is used. From the viewpoint of obtaining a tactile sensation and a fine writing effect, an ultrafine fiber of 0.5 dtex or less is preferable. At that time, the ultrafine fibers are obtained from direct spinning using a single component, or made from ultrafine fiber generating fibers composed of at least two kinds of polymers. The above-mentioned ultrafine fiber generating fiber is, for example, an extractable fiber in which the island component is fibrillated by the solvent or decomposition of the sea component, or a split fiber that is fibrillated into the ultrafine fiber made of each polymer mechanically or by a treatment agent. Etc. The ultrafine fiber-generating fiber is made into a short fiber or a long fiber having a fineness of 1 to 15 dtex through processing steps such as drawing, heat treatment, mechanical crimping, and cutting as necessary. Polymers constituting ultrafine fibers can be melt-spun of melt-spinnable polyamides such as 6-nylon, 66-nylon, 12-nylon, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, or copolymers thereof. At least one polymer selected from various polyesters is used. In addition, the component extracted or decomposed / removed by the extractable fiber is a polymer having a different solubility or decomposability with respect to the ultrafine fiber component and the solvent or decomposing agent, and having a low compatibility with the ultrafine fiber component, and under the spinning conditions. Therefore, it is necessary that the polymer has a lower melt viscosity or a lower surface tension than the ultrafine fiber component. For example, polyethylene, polystyrene, polyvinyl alcohol, or the like is used. In the present invention, it is more preferable to use polyvinyl alcohol that can be dissolved in hot water in view of environmental pollution, shrinkage characteristics during dissolution, and the like. Furthermore, the above ultrafine fibers can be colored with pigments typified by carbon black or the like or added with known fiber additives as long as the effects of the present invention are not impaired.
次に得られた短繊維あるいは長繊維を繊維絡合不織布とする。上記の繊維が短繊維であればカードで解繊し、ウェッバーを通してウエブを形成し、また、長繊維であればスパンボンド法などにより紡糸と同時にウエブを形成する。得られたウエブは、所望の重さ、厚さに積層し、次いで、必要に応じてニードルパンチ、高速水流などの公知の方法により仮絡合処理が行われる。上記ウエブの目付は、目的とする皮革様シートの目付に応じて設定されるが、８０〜２０００ｇ／ｍ２の範囲が好ましく、より好ましくは１００〜１５００ｇ／ｍ２の範囲が好ましい。なお、カーシート用途の場合、皮革様シートの強度を維持するために上記不織布に織編物を挿入することも可能である。なおその際の織編物は、特に限定することは無く、公知のポリマーからなる繊維を選ぶことができる。また、ニードルパンチの際は、織編物との絡合性確保の点から、織編物と積層する前のウエブに対し、パンチ数２０〜１００Ｐ／ｃｍ２の範囲のニードルパンチを施すことも可能である。なお、ここでいうパンチ数とは、ニードルパンチ工程を通してウエブの単位面積当たりに突き刺したフェルト針の累計本数であり、例えばフェルト針が１０本／ｃｍ２の密度で配置されたニードルボードをウエブへ５０回突き刺せば、そのニードルパンチ工程でのパンチ数は５００Ｐ／ｃｍ２である。 Next, the obtained short fiber or long fiber is used as a fiber-entangled nonwoven fabric. If the above fibers are short fibers, they are defibrated with a card and a web is formed through a webber. If long fibers are formed, a web is formed simultaneously with spinning by a spunbond method or the like. The obtained web is laminated to a desired weight and thickness, and then provisionally entangled by a known method such as needle punching or high-speed water flow, if necessary. The basis weight of the web is set according to the basis weight of the intended leather-like sheet, but is preferably in the range of 80 to 2000 g / m 2 , more preferably in the range of 100 to 1500 g / m 2 . In the case of car seat use, it is also possible to insert a woven or knitted fabric into the nonwoven fabric in order to maintain the strength of the leather-like sheet. In addition, the woven or knitted fabric at that time is not particularly limited, and fibers made of a known polymer can be selected. In addition, in the case of needle punching, from the viewpoint of securing the entanglement with the woven or knitted fabric, it is also possible to perform needle punching in the range of 20 to 100 P / cm 2 on the web before being laminated with the woven or knitted fabric. is there. The number of punches referred to here is the cumulative number of felt needles pierced per unit area of the web through the needle punching process. For example, a needle board in which felt needles are arranged at a density of 10 / cm 2 is applied to the web. When piercing 50 times, the number of punches in the needle punching process is 500 P / cm 2 .
得られた繊維絡合不織布の絡合空間に高分子弾性体を付与することが皮革様の風合いおよび充実感と機械的物性の向上の点で好ましく用いられる。高分子弾性体としては、風合いや充実感の点でポリウレタンが好ましい。なお、その際は溶剤に溶解したポリウレタン溶液を含浸後、水凝固し乾燥する方法や溶剤を用いない水系エマルジョンとしてポリウレタンを含浸後、乾熱凝固乾燥する方法のいずれも採用することができる。また、繊維絡合不織布と高分子弾性体との質量比が５０／５０〜９８／２となるように高分子弾性体を付与することが風合と機械物性を両立する点で好ましい。なお、繊維絡合不織布が極細繊維発生型繊維の場合は極細繊維化後の質量比として付与する。
更に繊維絡合不織布を構成する繊維が、極細繊維発生型繊維の場合には、公知の方法で高分子弾性体を付与する前あるいは後に極細可処理を行うことによって、皮革様シートを作製する。
Giving a polymer elastic body to the entangled space of the obtained fiber-entangled non-woven fabric is preferably used from the viewpoint of leather-like texture, fullness and mechanical properties. As the polymer elastic body, polyurethane is preferable in terms of texture and fullness. In this case, either a method of impregnating a polyurethane solution dissolved in a solvent and then water coagulating and drying, or a method of impregnating polyurethane as an aqueous emulsion without using a solvent and then drying and coagulating and drying can be employed. In addition, it is preferable to provide the polymer elastic body so that the mass ratio between the fiber-entangled nonwoven fabric and the polymer elastic body is 50/50 to 98/2 in terms of achieving both the texture and the mechanical properties. In addition, when a fiber entangled nonwoven fabric is an ultrafine fiber generation type fiber, it provides as mass ratio after ultrafine fiber formation.
Further, when the fiber constituting the fiber-entangled nonwoven fabric is an ultrafine fiber generating fiber, a leather-like sheet is produced by performing ultrafine treatment before or after applying the polymer elastic body by a known method.
上記方法で得られた皮革様シートでスエード調皮革様シートを作製する際には、スライス、バフィング等により所望の厚みに調整した後、表面をサンドペーパー等による公知の方法でバフィングすることにより上記繊維は起毛され、さらに染色することにより目的のスエード調皮革様シートとすることができる。また、銀面を有する銀付調皮革様シートを作成する際には、同様の方法で厚みを調整した後に、公知の方法により銀面層を形成することで得ることができる。 When producing a suede-like leather-like sheet with the leather-like sheet obtained by the above method, after adjusting to a desired thickness by slicing, buffing, etc., the surface is buffed by a known method such as sandpaper etc. The fibers are raised and dyed further to obtain the desired suede leather-like sheet. Moreover, when producing the grained leather-like sheet | seat which has a silver surface, after adjusting thickness by the same method, it can obtain by forming a silver surface layer by a well-known method.
本発明の難燃加工方法は、気泡を含有させた状態で難燃剤液を皮革様シート特にスエード調皮革様シートの裏面に塗布することが重要である。そして、難燃剤液中の難燃剤濃度を５〜６０質量％とすることによって、気泡の発現性と皮革様シートに対する難燃性の付与と風合の両立の点で好ましい。難燃剤濃度が５％未満になると、本難燃加工方法では十分な難燃性能を示すに必要な難燃剤を塗布することが困難となり易く、皮革様シートの難燃性効果が十分にならない傾向がある。また６０％よりも濃度が高くなると、塗布した難燃剤が皮革様シート内部に十分に浸透せず皮革様シート裏面付近に偏った状態で固化してしまい、皮革様シートの風合いが損なわれる。
また、環境に配慮することで、難燃剤液を難燃剤の水分散液または水溶液から構成することが好ましい。上記スエード調皮革様シートの裏面から泡状の難燃剤を浸透させるといった特殊な塗布方法を行うことによって始めて、スエード調皮革様シートの表層まで難燃剤が到達せず、表面の優れたタッチや風合いと難燃効果を維持することが可能となる。
In the flame-retardant processing method of the present invention, it is important to apply a flame retardant solution to the back surface of a leather-like sheet, particularly a suede-like leather-like sheet in a state of containing bubbles. And by making the flame retardant density | concentration in a flame retardant liquid into 5-60 mass%, it is preferable at the point of coexistence of the expression of a bubble, the provision of the flame retardance with respect to a leather-like sheet | seat, and a feeling. When the flame retardant concentration is less than 5%, it is difficult to apply the flame retardant necessary for exhibiting sufficient flame retardant performance with this flame retardant processing method, and the flame retardant effect of the leather-like sheet tends not to be sufficient. There is. On the other hand, if the concentration is higher than 60%, the applied flame retardant does not sufficiently penetrate into the leather-like sheet and solidifies in a state of being biased near the back of the leather-like sheet, and the texture of the leather-like sheet is impaired.
In consideration of the environment, the flame retardant liquid is preferably composed of an aqueous dispersion or an aqueous solution of the flame retardant. The flame retardant does not reach the surface layer of the suede leather-like sheet only by applying a special application method such as infiltrating the foam-like flame retardant from the back side of the suede leather-like sheet, and the surface has excellent touch and texture. It becomes possible to maintain the flame retardant effect.
本発明で使用する難燃剤としてはリン酸グアニジン系、リン酸カルバネート系、リン酸エステル系、リン酸エステルアミド系、ポリリン酸アンモニウム系など非ハロゲン系の難燃剤をあげることが出来る。そして、皮革様シートが難燃性を有するために必要な難燃剤の付着量は、難燃剤中のリン含有量にも左右されるため難燃剤の種類により異なるが、難燃剤の固形分濃度で１０〜１００ｇ/ｍ２の範囲で付与することが難燃性と風合を両立する点で好ましい。
なお、難燃剤を塗布する際は、処理後の皮革様シートからの難燃剤の脱落を防ぐために、本発明の効果を損なわない限り、水系ウレタンエマルションを難燃剤のバインダーとして混合させることも可能である。
Examples of the flame retardant used in the present invention include non-halogen flame retardants such as guanidine phosphate, carbanate phosphate, phosphate ester, phosphate ester amide, and ammonium polyphosphate. And the amount of flame retardant adhesion necessary for the leather-like sheet to have flame retardancy depends on the phosphorus content in the flame retardant, so it depends on the type of flame retardant, but the solid content concentration of the flame retardant It is preferable to apply in the range of 10 to 100 g / m 2 in terms of achieving both flame retardancy and texture.
In addition, when applying the flame retardant, in order to prevent the flame retardant from falling off from the leather-like sheet after the treatment, an aqueous urethane emulsion can be mixed as a flame retardant binder as long as the effect of the present invention is not impaired. is there.
また、強制的に気泡を含有させた状態での難燃剤液の見掛け密度が０．１〜０．６ｇ／ｃｍ３となる状態で例えば攪拌した後に塗布することが、難燃剤が裏面から浸透し表面に到達しないように調整しやすい点でより好ましい０．１ｇ/ｃｍ３以上とすることで、皮革様シートの体積あたりの難燃剤含有量を確保し、難燃性能を示すに必要な量の難燃剤を塗布することが可能となる。また０．６ｇ/ｃｍ３以下とすることで、気泡を含んだ状態を保持することが可能となる。なお、難燃剤の発泡方法としては機械発泡が挙げられるが、その際１〜２％の界面活性剤を発泡剤として加えることが好ましい。 In addition, the flame retardant permeates from the back surface, for example, after stirring in a state where the apparent density of the flame retardant liquid in the state of forcibly containing bubbles is 0.1 to 0.6 g / cm 3. By making it more preferable 0.1 g / cm 3 or more in terms of easy adjustment so as not to reach the surface, the amount of flame retardant per volume of the leather-like sheet is ensured, and the amount necessary to show flame retardant performance It becomes possible to apply a flame retardant. Moreover, it becomes possible to hold | maintain the state containing a bubble by setting it as 0.6 g / cm < 3 > or less. In addition, although a mechanical foaming is mentioned as a foaming method of a flame retardant, it is preferable to add 1 to 2% of surfactant as a foaming agent in that case.
難燃剤を皮革様シート裏面に塗布し、その付着量をコントロールする方法としては、皮革様シート上に気泡を有する難燃剤の水分散液または水溶液を吐出しそれをナイフにて付着量を管理する方法、または、皮革様シート裏面上に位置するメッシュロールの内部から外側へ吐出された気泡を有する難燃剤を、メッシュロールと皮革様シートの間のクリアランス調整あるいは印圧調整により付着量をコントロールしながら塗布する方法などを好ましく用いることができる。 As a method of applying the flame retardant to the back of the leather-like sheet and controlling the amount of adhesion, the aqueous dispersion or aqueous solution of the flame retardant with bubbles is discharged onto the leather-like sheet and the amount of adhesion is controlled with a knife. Control the amount of flame retardant with bubbles discharged from the inside or outside of the mesh roll located on the back side of the leather-like sheet by adjusting the clearance or printing pressure between the mesh roll and the leather-like sheet. A method of coating while applying can be preferably used.
難燃剤を塗布した後の皮革様シートの乾燥方法としては、テンター乾燥機など巾変化を制御しながらの乾燥が好ましい。 As a method for drying the leather-like sheet after applying the flame retardant, drying while controlling the width change such as a tenter dryer is preferable.
以下本発明の実施態様を実施例により説明するが、実施例における燃焼性の評価は社団法人自動車技術会制定がシート表皮用材料の試験方法(ＪＡＳＯ Ｍ ４０３−８８ )に記載する測定方法に従った。
また、難燃剤液の見掛け密度の測定方法は、発泡させた難燃剤液を５００ｍｌメスシリンダーに採取し、その体積と質量を測定することによって算出した。
Embodiments of the present invention will be described below by way of examples. The evaluation of flammability in the examples follows the measurement method described in the test method for sheet skin material (JASO M 403-88) established by the Society of Automotive Engineers of Japan. It was.
Moreover, the measuring method of the apparent density of a flame retardant liquid was computed by extract | collecting the foamed flame retardant liquid to a 500 ml graduated cylinder, and measuring the volume and mass.
［皮革様シートの製造］
ポリエステルを島成分として用い、高流動性低密度ポリエチレンを海成分として用いて、ポリエステル：ポリエチレン＝６５：３５の質量比でかつ島数５０で、３００℃で溶融複合紡糸を行って、海島型複合紡糸繊維を製造した後、７５℃の温水中で２．５倍に延伸し、繊維油剤を付与し、機械捲縮をかけて乾燥した後、５１ｍｍ長さに切断して、単繊維繊度５．０ｄｔｅｘのステープルを製造した。
上記で得られたポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いてクロスラップ法で常法にしたがって目付５２０ｇ／ｍ２のウエブを製造した後、両面から交互に合計で約２５００ｐ／ｃｍ２のニードルパンチングを行った。次いで、９０℃の熱水中で収縮処理した後、乾燥巾セットし、加熱された状態でカレンダーロールにてプレスすることで表面の平滑な絡合不織布を製造した。これにより得られた絡合不織布の目付は７６０ｇ／ｍ２および見掛密度は０．４８ｇ／ｃｍ３であった。
[Manufacture of leather-like sheets]
By using polyester as an island component, using a high-fluidity low-density polyethylene as a sea component, performing melt compound spinning at 300 ° C. with a mass ratio of polyester: polyethylene = 65: 35 and 50 islands, sea-island type composite After producing the spun fiber, it is stretched 2.5 times in warm water at 75 ° C., provided with a fiber oil agent, dried by mechanical crimping, cut into 51 mm length, and single fiber fineness 5. A 0 dtex staple was produced.
A web having a basis weight of 520 g / m 2 was produced according to a conventional method by a cross wrap method using a sea island type composite spun fiber staple comprising the polyester obtained above as an island component, and then a total of about 2500 p / m alternately from both sides. cm 2 needle punching was performed. Subsequently, after shrinking in hot water at 90 ° C., a dry width was set, and a entangled nonwoven fabric having a smooth surface was produced by pressing with a calender roll in a heated state. The basis weight of the entangled nonwoven fabric thus obtained was 760 g / m 2 and the apparent density was 0.48 g / cm 3 .
ポリカーボネート系ポリウレタン（日本ポリウレタン工業株式会社製「ニッポラン９９０Ｎ」）のジメチルホルムアミド（ＤＭＦ）溶液（固形分１４質量％）を、上記で得られた繊維絡合不織布の内部に含浸させ、次いで凝固浴［ＤＭＦ／水＝３０／２０（質量比）］中に浸漬して湿式凝固させた後、洗浄し、熱トルエン（温度９０℃）中に浸漬して、絡合不織布を形成している海島型複合紡糸繊維中のポリエチレン成分を溶出除去して極細繊維化した。得られた皮革様シートは、ポリエステル極細繊維の単繊維繊度が０．２デシテックスで厚さ１．３ｍｍであった。 A dimethylformamide (DMF) solution (solid content: 14% by mass) of polycarbonate-based polyurethane (“Nipporan 990N” manufactured by Nippon Polyurethane Industry Co., Ltd.) is impregnated inside the fiber-entangled nonwoven fabric obtained above, and then coagulated bath [ Dip / water = 30/20 (mass ratio)] is wet coagulated, washed, and dipped in hot toluene (temperature 90 ° C.) to form an entangled nonwoven fabric. The polyethylene component in the spun fiber was eluted and removed to make an ultrafine fiber. The obtained leather-like sheet had a monofilament fineness of the polyester ultrafine fiber of 0.2 dtex and a thickness of 1.3 mm.
上記で得られた皮革様シートの表面を所望の立毛長となるようにバッフィングしてスエード調皮革様シートとした後、下記の染色条件で染色して、染色したスエード調皮革様シートを製造した。
［スエード調皮革様シートの染色条件］
染 料 ：「Ｍｉｋｅｔｏｎ Ｐｏｌｙｅｓｔｅｒ Ｂｌｕｅ ＦＢＬ」 ３％ｏｗｆ（三井化学株式会社製）
染料温度：１２０℃
染料時間：６０分
浴 比 ： １：２０
染色装置：高圧液流染色機［（株）テクサム技研製「ＭＩＮＩ−ＪＥＴ Ｄ２００」）
After buffing the surface of the leather-like sheet obtained above to a desired napped length to make a suede-like leather-like sheet, it was dyed under the following dyeing conditions to produce a dyed suede-like leather-like sheet. .
[Dyeing conditions of suede leather-like sheet]
Dyeing: “Miketon Polyester Blue FBL” 3% owf (Mitsui Chemicals)
Dye temperature: 120 ° C
Dye time: 60 minutes bath Ratio: 1:20
Dyeing device: High-pressure liquid flow dyeing machine [“MINI-JET D200” manufactured by Tecsum Giken Co., Ltd.]
難燃剤発泡方法
リン酸グアニジン系難燃剤水溶液(ニッカファイノンP−２０５)に、カチオン界面活性剤からなる発泡剤(メイフォーマーＦ−２１０)を２％添加して、難燃剤濃度を５０％としたものを、見かけの密度が０．３ｇ/ｃｍ３になるよう機械発泡させた。
Flame retardant foaming method 2% of a foaming agent (Mayformer F-210) made of a cationic surfactant was added to a guanidine phosphate-based flame retardant aqueous solution (Nikkafinon P-205) to make the flame retardant concentration 50%. The material was mechanically foamed to an apparent density of 0.3 g / cm 3 .
難燃剤塗布方法
得られた気泡を有する難燃剤水溶液を開孔率４０％ 開孔径１１４０μｍのメッシュロール内部から吐出し、得られたスエード調皮革様シートの裏面に７０ｇ/ｍ２塗布した。なお、その際のメッシュロールとの間隔は０．４ｍｍになる調整した。その後連続的にピンテンター乾燥機で１４０℃、３分間加熱乾燥した。
得られたスエード調皮革様シートの表面には難燃剤によるぬめりが認められず優れた風合いを維持していた。また、難燃剤の塗布状態を確認する為に走査型電子顕微鏡で皮革様シートの断面を確認したところ、立毛面の近辺では難燃剤が存在せず、裏面から厚み方向に中央部分以下に存在していた。そして、燃焼試験結果は自消であり、十分な難燃性能が認められた。
Flame retardant application method The obtained flame retardant aqueous solution having air bubbles was discharged from the inside of a mesh roll having an aperture ratio of 40% and an aperture diameter of 1140 μm, and 70 g / m 2 was applied to the back surface of the obtained suede-like leather-like sheet. In addition, the space | interval with the mesh roll in that case was adjusted to be 0.4 mm. Thereafter, it was continuously dried with a pin tenter dryer at 140 ° C. for 3 minutes.
On the surface of the obtained suede-like leather-like sheet, no slimming due to the flame retardant was observed and an excellent texture was maintained. In addition, when the cross section of the leather-like sheet was confirmed with a scanning electron microscope to confirm the state of application of the flame retardant, there was no flame retardant near the raised surface, and it was present in the center part in the thickness direction from the back side. It was. And the combustion test result was self-extinguishing and sufficient flame retardance performance was recognized.
比較例１
実施例１と同様の方法で作成・染色したスエード調皮革様シートに、機械発泡処理を行わず、難燃剤液に気泡を含有させない以外は実施例１と同様の方法にて難燃剤を付与した。得られたスエード調皮革様シートは燃焼試験結果は自消であり、十分な難燃性能が認められた。しかしながら、難燃剤の塗布状態を確認する為に走査型電子顕微鏡で皮革様シートの断面を確認したところ、立毛面の近辺まで難燃剤が浸透存在しており、スエード調皮革様シートの表面には難燃剤によるぬめりがあり商品価値の低いものであった。
Comparative Example 1
A flame retardant was applied in the same manner as in Example 1 except that the suede-like leather-like sheet prepared and dyed in the same manner as in Example 1 was not subjected to mechanical foaming treatment and did not contain bubbles in the flame retardant liquid. . The obtained suede-like leather-like sheet was self-extinguishing as a result of the combustion test, and sufficient flame retardancy was recognized. However, when the cross section of the leather-like sheet was confirmed with a scanning electron microscope to confirm the application state of the flame retardant, the flame retardant permeated to the vicinity of the raised surface, and the surface of the suede-like leather-like sheet There was sliminess due to the flame retardant and the product value was low.
比較例２
実施例１と同様の方法で、作成・染色したスエード調皮革様シートに、固形分濃度１５％のリン酸グアニジン系難燃剤水溶液を含浸後ピックアップ率５０％になるようにマングルで絞り付着量を合わせた。その後連続的にピンテンター乾燥機で１００℃、７分間加熱乾燥した。得られたスエード調皮革様シートの燃焼試験結果は実施例と同様の問題のないものであったが、得られたスエード調皮革様シートの表面には難燃剤によるぬめりが認められ、また、風合の硬いものであった。
Comparative Example 2
In the same manner as in Example 1, the prepared and dyed suede leather-like sheet was impregnated with a guanidine phosphate-based flame retardant aqueous solution with a solid content concentration of 15%, and the amount of squeezed adhesion was adjusted with a mangle so that the pickup rate was 50%. Combined. Thereafter, it was continuously dried with a pin tenter dryer at 100 ° C. for 7 minutes. The results of the combustion test of the obtained suede-like leather-like sheet were free from the same problems as in the examples. However, the surface of the obtained suede-like leather-like sheet was found to be slimmed by a flame retardant. It was a hard one.
比較例３
実施例１と同様の方法で、作成・染色したスエード調皮革様シートの裏面側に、あらかじめリン酸グアニジン系難燃剤水溶液を含浸した織物を接着した。得られたスエード調皮革様シートの燃焼試験結果は実施例と同様の問題のないものであったが、天然皮革様の風合に劣るものであった。
Comparative Example 3
A fabric impregnated with an aqueous solution of a guanidine phosphate-based flame retardant in advance was bonded to the back side of the prepared and dyed suede-like leather-like sheet in the same manner as in Example 1. Although the combustion test result of the obtained suede-like leather-like sheet was free from the same problems as in Examples, it was inferior to the natural leather-like texture.
本発明の皮革様シートは、柔軟な風合いと優れた難燃性能を有するため、乗物用座席、クッションシート、ソファー、椅子などのインテリア製品の上張材などに特に有用である。
Since the leather-like sheet of the present invention has a soft texture and excellent flame retardancy, it is particularly useful as an upholstery material for interior products such as a vehicle seat, a cushion sheet, a sofa, and a chair.
Claims (7)
The flame-retardant leather-like sheet according to claim 5 or 6, wherein the leather-like sheet is a suede-like leather-like sheet made of an ultrafine fiber-entangled nonwoven fabric.
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| JP2010248683A (en) * | 2009-03-26 | 2010-11-04 | Toray Ind Inc | Leather-like sheet-shaped product and method for producing the same |
| KR101173798B1 (en) | 2009-06-30 | 2012-08-16 | 코오롱인더스트리 주식회사 | Artificial leather and method for manufacturing the same |
| CN102808333A (en) * | 2011-06-01 | 2012-12-05 | 现代自动车株式会社 | Method for producing synthetic leather having air permeability |
| WO2018003459A1 (en) * | 2016-06-28 | 2018-01-04 | 東レ株式会社 | Composite sheet product and method for manufacturing same |
| WO2022071049A1 (en) * | 2020-09-29 | 2022-04-07 | 東レ株式会社 | Artificial leather, production method therefor, and artificial leather backing material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101811584B1 (en) * | 2016-01-08 | 2017-12-26 | 김남일 | Method for manufacturing an artificial leather |
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| JP2005002512A (en) * | 2003-06-12 | 2005-01-06 | Toray Ind Inc | Artificial leather and method for producing the same |
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| JPH02133680A (en) * | 1988-11-14 | 1990-05-22 | Kuraray Co Ltd | Suede-like sheet |
| JPH05302273A (en) * | 1992-04-24 | 1993-11-16 | Toray Ind Inc | Artificial suede-like structure |
| JP2005002512A (en) * | 2003-06-12 | 2005-01-06 | Toray Ind Inc | Artificial leather and method for producing the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010248683A (en) * | 2009-03-26 | 2010-11-04 | Toray Ind Inc | Leather-like sheet-shaped product and method for producing the same |
| KR101173798B1 (en) | 2009-06-30 | 2012-08-16 | 코오롱인더스트리 주식회사 | Artificial leather and method for manufacturing the same |
| CN102808333A (en) * | 2011-06-01 | 2012-12-05 | 现代自动车株式会社 | Method for producing synthetic leather having air permeability |
| US20120308726A1 (en) * | 2011-06-01 | 2012-12-06 | Hyundai Motor Company | Method for producing synthetic leather having air permeability |
| US9644312B2 (en) * | 2011-06-01 | 2017-05-09 | Hyundai Motor Company | Method for producing synthetic leather having air permeability |
| WO2018003459A1 (en) * | 2016-06-28 | 2018-01-04 | 東レ株式会社 | Composite sheet product and method for manufacturing same |
| JPWO2018003459A1 (en) * | 2016-06-28 | 2019-04-11 | 東レ株式会社 | Composite sheet and manufacturing method thereof |
| WO2022071049A1 (en) * | 2020-09-29 | 2022-04-07 | 東レ株式会社 | Artificial leather, production method therefor, and artificial leather backing material |
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