JPS6134286A - Production of artificial leather sheet - Google Patents
Production of artificial leather sheetInfo
- Publication number
- JPS6134286A JPS6134286A JP15133784A JP15133784A JPS6134286A JP S6134286 A JPS6134286 A JP S6134286A JP 15133784 A JP15133784 A JP 15133784A JP 15133784 A JP15133784 A JP 15133784A JP S6134286 A JPS6134286 A JP S6134286A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- artificial leather
- elastic material
- polymer elastic
- high polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatment Of Fiber Materials (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野）
本発明は極めて柔軟な人工皮革シートの製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing highly flexible artificial leather sheets.
従来から、ｆｆ１ｌｉシートにバインダとして高分子弾
性体を付与した人工皮革シートを用い、表面に立毛を発
生させたスェード調、ベロア調、ヌパック調などの立毛
タイプ人工皮革、あるいは表面に高分子弾性体膜を付与
して銀面を形成さぼたいわゆる組付人工皮革などに加工
することはよく知られている。Conventionally, we have used artificial leather sheets in which a polymeric elastic material is added as a binder to the ff1li sheet, and we have used napped-type artificial leather such as suede-like, velor-like, and nupak-like textures with raised naps on the surface, or polymeric elastic materials on the surface. It is well known that a film is applied to form a silver surface and processed into so-called assembled artificial leather.
繊維シートに高分子弾性体を付与する方法により、高級
品扱いされている天然皮革に構造、性質を近斂せんとす
る人・工皮革の製造方法が多数提案されており、現在人
工皮革と呼ばれる製品のほとんどがこの方法によるもの
である。A number of methods have been proposed for manufacturing human and artificial leather that attempt to improve the structure and properties of natural leather, which is considered a luxury item, by adding polymeric elasticity to fiber sheets. Most of the products are made using this method.
バインダとして高分子弾性体を付与する理由としては、
主にｍ報シートのみでは得られない良好な強伸度特性、
引裂き強度、耐もみ性などの機械的性能を付与するとと
もに天然皮革によく似た表面形状、ｆｉｆｆｉ感、ボリ
ウーム感などを付与するためであり、人工皮革を製造す
る上で高分子弾性体バインダを用いることは必須とされ
てきた。The reason for adding an elastic polymer as a binder is as follows.
Mainly good strength and elongation properties that cannot be obtained with m-report sheets alone.
This is to provide mechanical properties such as tear strength and kneading resistance, as well as a surface shape similar to natural leather, as well as a firm and voluminous feel. It has been considered necessary to use it.
ところが、この方法は繊維シートに付与された高分子弾
性体の粗大な皮膜が楳軒ｔあるいは楳ｍ束間に介在して
バインダ効果を発揮し、上記性能などに寄与するもので
あり、満足する上記性能などを有する人工皮革ををんと
すれば用途によっては人工皮革の１つの重要な性能とな
る柔軟性、ドレープ性、表面タッチなどの風合性能を損
うという問題点がある。すなわらかかる方法においては
、機械的性能と風合性能の相反する性能を同時に満足さ
せることは極めて困難であり、そのため従来の人工皮革
では天然皮革の分野に見られるような高度な柔軟性を要
求されるドレス、ブラウス、シャツなどの薄地衣料用途
などには適さないとされてきた。However, this method is satisfactory because the coarse film of the polymeric elastic material applied to the fiber sheet acts as a binder by intervening between the tufts or tufts, contributing to the above-mentioned performance. If artificial leather having the above-mentioned properties is used, there is a problem in that, depending on the use, the texture performance such as flexibility, drapability, and surface touch, which is one of the important performances of artificial leather, may be impaired. In other words, with this method, it is extremely difficult to simultaneously satisfy the contradictory properties of mechanical performance and texture performance, so conventional artificial leather cannot achieve the high degree of flexibility seen in the field of natural leather. It has been considered that it is not suitable for the required thin clothing applications such as dresses, blouses, and shirts.
この問題を解決するにはシート中の高分子弾性体バイン
ダの構造あるいは付着状態を改良することが有効なポイ
ントとされ、今まで高分子弾性体のイリ与および１１λ
固工程において次のような提案がなされてきた。すなわ
ち
１）高分子弾性体の凝固方法を湿式凝固とし、多孔化構
造とする方法。To solve this problem, it is considered effective to improve the structure or adhesion state of the polymeric elastic binder in the sheet.
The following proposals have been made in the hardening process. Namely, 1) A method of using wet coagulation as the coagulation method of the polymer elastic body to form a porous structure.
２）湿式凝固方法において、
温度差多段凝固とする方法、２種以上の高分子弾性体を
用いて凝固速度差を利用する方法、高分子弾性体中に凝
固調整剤あるいは構造調整剤を添加する方法、２種以上
の高分子弾性体を用いて一部を溶解させる方法などによ
り高分子弾性体膜を特殊多孔化４Ｒ造とする方法、ある
いは凝固浴中で凝固液を噴射、流動又は振動さ往ながら
凝固を行なう方法。2) In the wet coagulation method, there are several methods: multi-stage solidification with temperature differences, using two or more types of elastomer polymers to utilize differences in solidification rate, and adding a coagulation modifier or structure modifier to the elastomer polymer. A method of making a polymer elastic membrane into a special porous 4R structure by partially dissolving two or more types of polymer elastic materials, or a method in which a coagulation liquid is sprayed, flowed or vibrated in a coagulation bath. Traditionally, a method of coagulation.
３）予め繊維シートに可溶性高分子物質を付与し、その
後高分子弾性体をイ」与、凝固してから該高分子物質を
抽出し、繊維と高分子弾性体の間にすき間をもたせたい
わゆるトンネル構造とする方法。3) A so-called method in which a soluble polymer substance is applied to a fiber sheet in advance, then an elastic polymer substance is applied, the polymer substance is extracted after coagulation, and a gap is created between the fibers and the elastic polymer substance. A method of creating a tunnel structure.
などがある。and so on.
しかし、これらの提案はいずれも柔軟化効果が小さく、
あえてこれらの方法にＪ二り高度に柔軟性を付与しよう
とずれば機械的性能、ｌｆｆ１感、外観品位、加工上の
寸法安定性、耐毛羽落性などが著しく低下し、実用に供
し１ｑないものになってしまうのである。However, all of these proposals have little flexibility effect;
If one dares to impart a higher degree of flexibility to these methods, the mechanical performance, lff1 feel, appearance quality, dimensional stability during processing, fuzz resistance, etc. will deteriorate significantly, making it impossible to put it to practical use. It becomes something.
従って、今だ良好な機械的性能などを維持しつつ充分な
風合性能を付与する方法は見つかっていないのが現状で
ある。Therefore, at present, no method has yet been found to provide sufficient hand feel while maintaining good mechanical performance.
（発明が解決しようとする問題点）
本発明は繊維シートに高分子弾性体バインダを付与して
成る人工皮革シートの製造方法において、良好な機械的
性能を得んとすれば、風合性能が低下するという従来技
術では避けられない問題点を解決し、機械的性能と風合
性能の相反する２つの性能を同時に満足する人工皮革シ
ートを製造する方法を提供するものである。(Problems to be Solved by the Invention) The present invention provides a method for manufacturing an artificial leather sheet in which a polymeric elastic binder is applied to a fiber sheet. The object of the present invention is to provide a method for manufacturing an artificial leather sheet that solves the problem of deterioration that cannot be avoided with conventional techniques and simultaneously satisfies two conflicting performances: mechanical performance and texture performance.
Ｃ問題点を解決するための手段）
本発明者らは、上記問題点に対して鋭意検討した結果、
本発明を見出した。すなわち本発明は、１１１シートに
高分子弾性体を付与してなる人工皮革シートの製造方法
において、繊維シートに付与された高分子弾性体液が完
全凝固するまでに高速流体処理を施ずことを特徴とする
人工皮革シートの製造方法、
に関するものである。Means for Solving Problem C) As a result of intensive studies by the present inventors regarding the above problems,
The present invention has been discovered. That is, the present invention is a method for manufacturing an artificial leather sheet formed by adding a polymeric elastic body to a 111 sheet, characterized in that high-speed fluid treatment is not performed until the polymeric elastic body fluid applied to the fiber sheet is completely solidified. The present invention relates to a method for producing an artificial leather sheet.
本発明に使用される繊維シートは特に限定がなく、従来
公知の方法で製造される二−ドルパンチ不織布、ウォー
タージェットパンチ不織布、織物或いは編物に短繊維を
絡ませ一体化したシート、繊維をＦｉ＆希したシート、
植毛シート、長繊維不織布、織物、編物などいずれでも
適用できる。繊維の絡み合いの形態から柔軟性、ドレー
プ性が得難いシートＩＭ造である不織布は、特に効果的
に本発明を達成することができる。The fiber sheet used in the present invention is not particularly limited, and includes a needle punch nonwoven fabric produced by a conventionally known method, a water jet punch nonwoven fabric, a sheet made by entangling short fibers with a woven or knitted fabric, and a sheet made by intertwining short fibers with a woven or knitted fabric, and a sheet made by intertwining short fibers with a woven or knitted fabric. sheet,
It can be applied to flocked sheets, long fiber nonwoven fabrics, woven fabrics, knitted fabrics, etc. The present invention can be particularly effectively achieved with nonwoven fabrics having a sheet IM structure, in which flexibility and drapability are difficult to obtain due to the form of intertwined fibers.
これらを構成する繊維としてはポリアミド、ポリエステ
ル、ポリエーテル、ポリエステルポリエーテル、ポリエ
ステルポリアミド、ポリアクリル、ポリピロプレンなど
の合成繊組を初めとして、木綿、羊毛、麻、絹などの天
然繊維、レーヨンなどの再生繊維、アセテートの半合成
繊組などの単独またはそれらの少なくとも２種以上から
なる混合ｍ １１を使用できる。特にポリエチレンテレ
フタレート、ナイロン６、ナイロン６６は得られる製品
の物性および実用性能の点からも好ましい。The fibers that make up these include synthetic fibers such as polyamide, polyester, polyether, polyester polyether, polyester polyamide, polyacrylic, and polypyroprene, as well as natural fibers such as cotton, wool, hemp, and silk, and recycled rayon. It is possible to use fibers, acetate semi-synthetic fibers, etc. alone, or a mixture of at least two or more thereof. In particular, polyethylene terephthalate, nylon 6, and nylon 66 are preferred from the viewpoint of the physical properties and practical performance of the resulting product.
本発明に用いる繊維の太さは人工皮革としての性能ずな
わら柔軟性、感触、ドレープ性、外観品位、強度特性な
どを高めるために２．０デニール以下が好ましく、特に
好ましくは０．５デニール以下である。このような極１
１Ｉ繊紺を得る手段としてはスーパードロー法、フラッ
シュ紡糸法、ジ工ット紡糸法、複合紡糸法などの公知の
方法が用いられ、中でも２種以上のポリマを用いて紡糸
する海島型の高分子配列体繊維、混合紡糸ｍＨ，剥離型
繊維などの複合ｌｌ１Ｉ［Ｅは本発明に好適な繊維であ
る。The thickness of the fibers used in the present invention is preferably 2.0 denier or less, particularly preferably 0.5 denier, in order to improve the performance as artificial leather, such as flexibility, feel, drapability, appearance quality, strength characteristics, etc. It is as follows. Such pole 1
Known methods such as the super draw method, flash spinning method, jet spinning method, and composite spinning method are used to obtain the 1I navy blue fiber. Composite ll1I[E such as molecular array fibers, mixed spun mH, and peelable fibers are suitable fibers for the present invention.
かかるＵ５Ｎシートを用いて高分子弾性体を付与するが
、本発明に用いられる高分子弾性体としては、例えば、
ポリウレタン類、ポリブタジェン、ポリイソプレン、ポ
リクロロプレン、ポリアクリル系、フッ素樹脂系エラス
トマ類などの合成ゴム類あるいは天然ゴム類の１種また
は２種以上が使用される。その中でポリウレタン類は本
発明に好適な高分子弾性体である。この高分子弾性体は
溶液又はエマルジョン、ディスパージョンなどにして繊
維シートに浸漬、塗布、スプレーなどの方法によって付
与される。Such a U5N sheet is used to provide an elastic polymer, and the elastic polymer used in the present invention includes, for example,
One or more synthetic rubbers or natural rubbers such as polyurethanes, polybutadiene, polyisoprene, polychloroprene, polyacrylic and fluororesin elastomers are used. Among them, polyurethanes are suitable polymeric elastomers for the present invention. This polymeric elastomer is applied as a solution, emulsion, dispersion, etc. to the fiber sheet by methods such as dipping, coating, and spraying.
楳紺シートに対する高分子弾性体の付与ｍは、弾性体の
種類、製品シートの用途によって適宜選択ずればよいが
、通常、実質残存ｍ維に対して固形分で５〜１５０％で
あり、好ましくは１０〜１００％である。高分子弾性体
の付与処理は１回のみの処理でも、２回以上の多段処理
であってもかまわない。すなわら、１段処理によって付
与されたシートに更に同４ｉＩ！あるいは異種の高分子
弾性体を付与する処理であってもよい。The amount m of the polymeric elastic material applied to the mapped dark blue sheet may be selected as appropriate depending on the type of elastic material and the use of the product sheet, but it is usually 5 to 150% in terms of solid content based on the remaining m fibers, and is preferably is 10-100%. The process of applying the polymeric elastic body may be performed only once or may be performed in multiple stages of two or more times. In other words, the same 4iI! is added to the sheet added by the first stage process! Alternatively, it may be a process of imparting different types of polymer elastic bodies.
繊維シートに高分子弾性体を付与した後、高速流体処理
を施す。高速流体処理は繊維シートに付与された高分子
弾性体が完全凝固するまでに行なう。これは高分子弾性
体が完全凝固するまでに高速流体を噴射することにより
、繊維および／又は繊維束の３次元格合が強化されると
ともに、繊維シート中の空隙に充填された高分子弾性体
液が噴出流体によりシート内に小さく分散されながら繊
維間、繊組束間および／又は繊維束内ｑ細部まで押込ま
れて付着し、高分子弾性体７部雑あるいは高分子弾性体
／繊維束のバインダ効果を高めるのである。すなわち該
処理はシート内部の高分子弾性体膜を微細に分割する作
用でシートに柔軟性を付与し、高絡合化されたシートに
高分子弾性体を１部に押込む作用で強度特性を付与する
のである。After applying the polymer elastic material to the fiber sheet, it is subjected to high-speed fluid treatment. The high-speed fluid treatment is performed until the polymer elastic material applied to the fiber sheet is completely solidified. By injecting a high-speed fluid until the polymeric elastic body is completely solidified, the three-dimensional lattice of fibers and/or fiber bundles is strengthened, and the polymeric elastic body fluid fills the voids in the fiber sheet. is dispersed in a small amount within the sheet by the ejected fluid, and is pushed and adhered to the fine details between the fibers, between the fiber bundles, and/or within the fiber bundle, and binds the elastic polymer body or the binder of the elastic polymer body/fiber bundle. It increases the effectiveness. In other words, this treatment imparts flexibility to the sheet by finely dividing the elastic polymer film inside the sheet, and improves strength properties by forcing the elastic polymer into one part of the highly entangled sheet. It gives.
しかも加工上の寸法安定性を良くし、立毛タイプ人工皮
革においては毛羽落ちの少ない製品とすることができる
。更に該処理により、高速噴出流が瞬時にシート内部に
浸透するために、高能率かつ、均一な凝固ができ、更に
は溶媒などの抽出を迅速に行なうことができる。In addition, the dimensional stability during processing is improved, and napped type artificial leather can be made into a product with less fluffing. Furthermore, by this treatment, the high-speed jetting flow instantaneously permeates into the interior of the sheet, so that highly efficient and uniform coagulation can be achieved, and furthermore, the solvent and the like can be extracted quickly.
本発明は上述の如く、該処理により従来の人工皮革シー
トと比較してシート内部の繊ｌｆｆ１／高分子弾性体の
尉造を全く異なるものにして、茗しい柔軟効果をもたら
すのである。As described above, the present invention uses this treatment to make the structure of the fiber lff1/polymer elastomer inside the sheet completely different from that of conventional artificial leather sheets, thereby providing a gentle soft effect.
高速流体処理は、例えば高速噴出流として細いオリフィ
スから高圧下で噴出された液体類、主として水、温水又
は熱水によるいわゆるウォータージェットパンチ法ある
いは高速噴出流として細いオリフィスから高圧下で噴出
された気体類、主として空気又は熱気によるいわゆるエ
アジェツトパンチ法などがあり、いずれの方法も本発明
に適用できる。流体の噴射エネルギ効率からすると、噴
出が：体として液体類を用いる方が好ましい。特に渇、
熱水で行なうと、凝固が更に促進されるため、処理時間
の短縮が可能となる。また同時にシートの収縮が燻るた
め収縮処理を別に行なう必要がなくなるという利点もあ
る。かかる点から、好ましくは６０℃以上、更に好まし
くは８５℃以上の混、熱水が良い。High-speed fluid processing includes, for example, liquids ejected under high pressure from a narrow orifice as a high-speed jet stream, the so-called water jet punch method using mainly water, hot water, or hot water, or gases ejected under high pressure from a narrow orifice as a high-speed jet stream. There are various methods, mainly the so-called air jet punch method using air or hot air, and any of these methods can be applied to the present invention. From the viewpoint of fluid ejection energy efficiency, it is preferable to use liquids as the ejection material. Especially thirst,
When hot water is used, coagulation is further promoted, so that the processing time can be shortened. At the same time, there is also the advantage that there is no need to perform a separate shrinkage treatment because the sheet shrinks. From this point of view, it is preferable to use hot water at a temperature of 60°C or higher, more preferably 85°C or higher.
なお、液体類には、厚擦損失の防止やＷｎ射効果を上げ
る目的で添加剤を加えてもよい。Note that additives may be added to the liquids for the purpose of preventing thick friction loss and increasing the Wn radiation effect.
該処理に用いる噴射流体は、付与する高分子弾性体によ
って異なり、該高分子弾性体を溶解させないで、しかも
凝固を促進゛するものが好ましい。The jetting fluid used for this treatment varies depending on the elastomeric polymer to be applied, and is preferably one that does not dissolve the elastomer and promotes coagulation.
すなわち、該高分子弾性体の非溶媒でかつ高分子弾性体
の溶媒とは混和性のあるものが好ましい。That is, it is preferable to use a solvent that is a non-solvent for the elastic polymer and is miscible with the solvent for the elastic polymer.
高速流体処理に用いるオリフィスの径は通常、０．０５
〜３．００ｍｍであり、好ましくは０．１〜１．０作が
用いられる。オリフィスの形状はいかなるものであって
もかまわないが、通常円形のものが採用される。オリフ
ィスは可能な限り高密度に配賀するのが好ましい。流体
を押出す圧力は一般には５〜５００に９／ａｌ、りＹま
しくは１０〜３００ ｋｉ ／ ａｌが採用される。噴
射圧力が過少であると本発明の目的を十分達成しにくく
、過大でも処理シートの供械的性能の低下を招きやすく
、また処理跡がでやすく、シートの表面品位が損われる
ことがある。この噴射処理はオリフィスを揺動しながら
、特に×軸（シートの幅方向）およびＹ＠（シートの進
行方向）の両軸揺動させながら行なうのが好ましい。こ
れは処理跡を解消するのに極めて有効である。更に該処
理は片面からあるいは両面から行なっても、また１回処
理であっても２回以上の処理であってもよい。The diameter of the orifice used for high-speed fluid processing is typically 0.05
~3.00 mm, preferably 0.1 to 1.0 mm. The orifice may have any shape, but a circular one is usually adopted. It is preferred that the orifices be distributed as densely as possible. The pressure for extruding the fluid is generally 5 to 500 to 9/al, or preferably 10 to 300 ki/al. If the injection pressure is too low, it will be difficult to sufficiently achieve the object of the present invention, and if the injection pressure is too high, the mechanical properties of the treated sheet will likely deteriorate, and treatment marks will likely appear, which may impair the surface quality of the sheet. This injection process is preferably carried out while swinging the orifice, particularly while swinging the orifice in both the x axis (width direction of the sheet) and the Y@ (sheet traveling direction) axis. This is extremely effective in eliminating processing marks. Further, the treatment may be performed from one side or both sides, and may be performed once or twice or more.
オリフィスと被処理シート面の距離は通常１０〜１００
ｍｍである。距離が過大になると噴出流体のエネルギ損
失が大きくなって処理効率を悪くし、過少のときは流体
噴射跡を生ずる原因になる。また、高速流体の噴射角度
はシート面に対して通常９０度±４５度であるが、処理
効果あるいは処理シートの用途などに応じて適宜調整す
ればよい。The distance between the orifice and the sheet surface to be treated is usually 10 to 100 mm.
It is mm. If the distance is too large, the energy loss of the ejected fluid will increase, resulting in poor processing efficiency, and if the distance is too short, it will cause fluid ejection marks. Further, the injection angle of the high-speed fluid is usually 90 degrees ±45 degrees with respect to the sheet surface, but may be adjusted as appropriate depending on the processing effect or the use of the processing sheet.
高速流体処理の及ぶシート内への深さすなわち有効到達
深度は少なくともシートの厚みの約１／４以上であるこ
とが好ましく、それ以上であればシートを貫通してもか
まわない。シートの約１／４以上の深さに噴出流体を浸
透させるための流体の速度は、シートの厚さ、密度ある
いは流体の密度、性質などによって一概に言えないが、
一般には２０ｍ／秒以上であることが好ましく、更には
５０ｍ／秒以上であることが特に好ましい。ここで有効
到達深度とは、シート中に固着した高分子弾性体の形状
又は大きさ、繊維束、繊維の向き、繊キ１ｔの絡み状態
、８ｊＡ紺と高分子弾性体の位置関係、その他高速流体
の通過跡など噴射された高速流体により、何らかの現象
の変化を伴なう深さをさす。It is preferable that the depth into the sheet, that is, the effective depth reached by high-speed fluid treatment, is at least about 1/4 of the thickness of the sheet or more, and the sheet may be penetrated as long as it is greater than that. The speed of the fluid to infiltrate the ejected fluid to a depth of about 1/4 or more of the sheet cannot be determined with certainty depending on the thickness and density of the sheet or the density and properties of the fluid.
Generally, the speed is preferably 20 m/sec or more, and particularly preferably 50 m/sec or more. The effective reaching depth here refers to the shape or size of the elastic polymer body fixed in the sheet, the fiber bundle, the direction of the fibers, the state of entanglement of 1 t of fibers, the positional relationship between the 8jA navy blue and the elastic polymer body, and other high-speed Refers to the depth at which some kind of phenomenon changes due to jetted high-speed fluid, such as traces of fluid passage.
該処理条件は人工皮革の用途、目的に応じて適宜選んで
調整すればよいが、処理条件があまりにも弱いと本発明
は達成できない。The processing conditions may be appropriately selected and adjusted depending on the use and purpose of the artificial leather, but if the processing conditions are too weak, the present invention cannot be achieved.
これまでの凝固浴中で液体を噴射する例としては、被処
理シートを凝固浴中に浮かせることによりロールなどの
支持体に接触させないで搬送する方法（持分ｎｆ（４８
−９２３３） 、凝固浴中の被処理シート表層の高濃度
に溶媒を含んだ液層との液を順次置換し凝固を促進する
方法（特公昭５５−２６２２４＞ 、工程張力を小さく
するために、凝固液に流れを生じさせ、その流れに沿っ
て被処理シートを搬送する方法（特公昭５６−１６２２
２＞などが提案されている。しかし、これらの提案はい
ずれも本発明の如くシート内部まで噴出流体を瞬時に浸
透させ、シート内部の高分子弾性体／ｌＩ紺の４１１Ｘ
造を変えて柔軟化を図るものではなく、本発明とは思想
および内容とも全く異なるものである。As an example of conventional jetting of liquid in a coagulation bath, there is a method in which the sheet to be processed is floated in a coagulation bath and conveyed without contact with a support such as a roll (equity nf (48
-9233), A method of promoting coagulation by successively displacing the liquid layer containing a high concentration of solvent on the surface layer of the sheet to be processed in a coagulation bath (Japanese Patent Publication No. 55-26224>, In order to reduce the process tension, A method of creating a flow in the coagulating liquid and transporting the sheet to be processed along the flow (Japanese Patent Publication No. 56-1622)
2> etc. have been proposed. However, in all of these proposals, as in the present invention, the ejected fluid instantly penetrates into the inside of the sheet, and the polymer elastic material inside the sheet / lI navy blue 411X
This does not attempt to make the structure more flexible, and is completely different in concept and content from the present invention.
高速流体処理は繊維シートに付与された高ｊ）子弾性体
が完全凝固するまでであれば何時でも処理が可能であり
、高分子弾性体が付与された直後でも、又一旦凝固浴中
に導かれて凝固途中にあるものでもかまわない。更には
高速流体処理は１段処理であっても、又聞に凝固工程を
はさむ２段以上の処理であってもよい１゜
高速流体処理の前ｊ５よび／又は後に行なう高分子弾性
体の凝固処理は、高分子弾性体の溶媒とは混和性のある
非ＦＪ媒を主体にした液体中に浸漬して凝固する湿式凝
固法、ドライヤなどにより高分子弾性体の溶媒を直接除
去して固化する乾式凝固法のいずれの方法も適用できる
し、又これらを組合ぜた方法も可能である。凝固は１段
処理であっても又２段以上の処理によって達成されても
よい。High-speed fluid treatment can be carried out at any time until the high molecular weight elastic material applied to the fiber sheet is completely solidified. It does not matter if it has been dried and is still solidifying. Furthermore, the high-speed fluid treatment may be a single-stage process or may be a two- or more-stage process with a coagulation step in between. Processing is a wet coagulation method in which the material is immersed in a liquid mainly consisting of a non-FJ medium that is miscible with the solvent of the polymeric elastomer, and solidification is performed by directly removing the polymeric elastomer's solvent using a dryer, etc. Any of the dry coagulation methods can be applied, and a combination of these methods is also possible. Solidification may be achieved in a single stage process or in two or more stages.
１式凝固を行なう場合、高速流体処理は凝固浴内あるい
は凝固浴外のいずれでもかまわないが、凝固浴外で行な
う方がより好ましい。その理由は高圧で噴Ｇ’ｌされた
高速流体エネルギーが浴中であれば著しく減じられてし
まい、シート内部まで噴出流体を浸透させることが困難
となるためである。When carrying out one-stage coagulation, the high-speed fluid treatment may be carried out either inside or outside the coagulation bath, but it is more preferable to carry out the treatment outside the coagulation bath. The reason for this is that the energy of the high-speed fluid jetted out at high pressure is significantly reduced in the bath, making it difficult for the jetted fluid to penetrate into the interior of the sheet.
高速流体処理／？Ｕ固の組合せ処理は数種類の工程が可
能であるが、これらの中で特に柔軟な人工皮革シートを
１ｑる方法を挙げれば、繊維シートに高分子弾性体を付
与した直後、高分子弾性体の溶媒に対して混合性のある
非溶媒を主体とした液体を噴出流体とする？３速流体処
理を表裏両面から行ない、噴出流体と同じ液体からなる
凝固浴中に浸漬し、凝固した後残存溶媒を抽出、乾燥し
て人工皮革シートを４ｇる方法である。この場合、噴出
流体、凝固浴とも凝固をｔｉｌ＋害しない程度に高分子
弾性体に用いた溶媒が合まれでもかまわない。又繊維シ
ートに高分子弾性体を付与する前に、凝固液に溶解し、
且つ高分子弾性体の溶媒によって変形、膨潤しない高分
子物質例えば高分子弾性体としてポリウレタンを用いる
場合、ポリビニールアルコール及びその変成体、カルボ
キシメチルセルロース、カゼイン、ポリエチレンオキサ
イド等を付与してもかまわない。High-speed fluid processing/? Several types of processes are possible for the U-hardening process, but among these, one method for producing 1q of particularly flexible artificial leather sheets is to apply the polymer elastic material to the fiber sheet immediately after applying the polymer elastic material. Is the jetting fluid a liquid mainly consisting of a non-solvent that is miscible with the solvent? This is a method in which three-speed fluid treatment is carried out on both the front and back sides, immersed in a coagulation bath made of the same liquid as the ejected fluid, and after coagulation, the remaining solvent is extracted and dried to yield 4 g of artificial leather sheet. In this case, the ejected fluid and the coagulation bath may be mixed with the solvent used for the polymeric elastomer to the extent that the coagulation is not impaired. Also, before adding the polymer elastic body to the fiber sheet, it is dissolved in a coagulation liquid,
In addition, when using a polymer material that does not deform or swell by the solvent of the polymer elastomer, such as polyurethane as the polymer elastomer, polyvinyl alcohol and modified products thereof, carboxymethyl cellulose, casein, polyethylene oxide, etc. may be added.
この方法によれば従来の高分子弾性体付与／湿式凝固に
比べて極度にシートを柔軟にすることができるのである
。他の８速流体処１１！／凝固の組合せ処理を選んだ場
合でも、高速流体処理による柔軟効果はきわめて大きい
のである。According to this method, the sheet can be made extremely flexible compared to conventional polymer elastic material application/wet coagulation. Other 8 speed fluid processing 11! Even if a combination treatment of /solidification is selected, the flexibility effect of high-speed fluid treatment is extremely large.
かかる処理を施した人工皮革シートを用いて、従来より
きわめて柔軟でしかも良好な機械的性能を有する立毛タ
イプ人工皮革あるいは組付人工皮革を製造することがで
きる。Using the artificial leather sheet subjected to such treatment, raised type artificial leather or assembled artificial leather which is extremely flexible and has better mechanical performance than conventional ones can be produced.
本発明において、高速流体処理の前後において人工皮革
を製造するのに公知とされているシート化工程、収縮、
型態固定剤の付与、繊維の極細化、熱プレス、熱処理、
スライス、パフ、染色、銀面（＝ｊ与、仕上剤処理など
のイづ加工程を適宜設けることにより、目的、用途に応
じた人工皮革に加工できるのである。In the present invention, before and after high-speed fluid treatment, the sheeting process, shrinkage,
Adding shape fixing agent, ultrafine fiber, heat press, heat treatment,
By appropriately performing processing steps such as slicing, puffing, dyeing, grain finishing, and treatment with finishing agents, it is possible to process artificial leather according to the purpose and use.
次に本発明に係る実施例を示す。 Next, examples according to the present invention will be shown.
本発明にお（ブる製品の測定は以下の方法による。The measurement of the products according to the present invention is carried out by the following method.
（１）引張強カニＪＩＳ−Ｌ１０７９の５．１２゜（２
）剛軟度： Ｊ Ｔ５−Ｌｌ ０７９の５．１７のＡ法
（３）ドレープ係数：ＪＩＳ−１１０７９の５゜１７の
Ｆ法
（４）引裂強カニＪＩＳ−Ｌ１０７９の５．１４のＣ法
特に説明のない限り「割合」及び「％」は全てｍｍに基
づく。(1) Tensile strength Crab JIS-L1079 5.12° (2
) Bending resistance: A method of 5.17 of J T5-Ll 079 (3) Drape coefficient: F method of 5.17 of JIS-11079 (4) Tear strength method C of 5.14 of JIS-L1079 Especially All "percentages" and "%" are based on mm unless otherwise stated.
実施例１
島成分としてポリエチレンテレフタレート、海成分とし
てポリスチレンからなる成分比５０１５０、太さ３．０
デニール、島数３６、カット長５１ｍｍ、捲縮数１５〜
１８山／インチのへ分子配列体Ｉｎ維からなる原綿を用
いてカード、クロスラッパーを通して目付６００ Ｑ
／ Ｔ１１”のウェッブを作成した。該ウェッブに針密
ｆＪｉ３０００本／ｄのニードルパンヂを行ない目付６
１００／Ｔｌ＋”、見掛密度０．２２１ｃ＋／ｆｆｌの
不織布繊維シートを得た。Example 1 Component ratio 50150, thickness 3.0 consisting of polyethylene terephthalate as the island component and polystyrene as the sea component
Denier, number of islands 36, cut length 51mm, number of crimps 15~
Using raw cotton made of hemolecular array In fiber with 18 threads/inch, it is passed through a card and a cross wrapper to a fabric weight of 600 Q.
/ T11" web was created. The web was needle punched with a needle density fJi of 3000 pieces/d to a fabric weight of 6.
A nonwoven fiber sheet having an apparent density of 0.221c+/ffl and an apparent density of 0.221c+/ffl was obtained.
この不織布繊維シートを９５℃の熱水に通して収縮した
。この時の面積収縮率は３２％であった。This nonwoven fiber sheet was shrunk by passing it through hot water at 95°C. The area shrinkage rate at this time was 32%.
次いでポリビニルアルコールの１２％水溶液を含浸して
繊維シートに対して固形分でポリビニルアルコールを２
２％付与した。該シートをトリクレンで洗浄して、海成
分を除去して乾燥した。次いで該シートをポリウレタン
の１２％ジメチル小ルムアミド溶液中に浸漬した後マン
グルでニップしてポリウレタン溶液を付与した。この直
後シー＋−の上面力目ジ水を高速噴出流体として用いる
高速流４ホ処理を行ない、続いて下面から同じ処理を行
なった。この高速流体処理条件はオリフィス径０゜２５
閘φ、オリフィスピッチ２．５ｍｍ、水圧１００ｋｇ１
０＋ｒ、鳴出流体速麿１４１１１１／秒、揺動幅１０ｍ
、３ｍ動ザイクル３回／秒、処理速度２５０ｍ／分であ
り、この時噴出流体はシートを貫通した。Next, the fiber sheet is impregnated with a 12% aqueous solution of polyvinyl alcohol to give a solid content of 2% polyvinyl alcohol.
2% was given. The sheet was washed with trichlene to remove sea components and dried. The sheet was then dipped in a 12% dimethyl lumamide solution of polyurethane and then nipped with a mangle to apply the polyurethane solution. Immediately after this, a high-speed flow 4-hole treatment using water as a high-speed ejection fluid was performed on the upper surface of Sea+-, and then the same treatment was performed from the lower surface. This high-speed fluid processing condition is for an orifice diameter of 0°25.
Lock φ, orifice pitch 2.5mm, water pressure 100kg1
0+r, Naride fluid velocity 141111/sec, swing width 10m
, 3 m motion cycles 3 times/sec, processing speed 250 m/min, and the ejected fluid penetrated the sheet.
この処ＰＩ！４１３０℃の水中に導いてポリウレタンを
凝固し、次いで熱水中でポリビニルアルコール及びジメ
チルホルムアミドを洗浄し除去した。これらの処理によ
るポリウレタンの＜”Ｊ着ｍは繊維１００部に対して３
０部であった。次いでこのシートを面方向にスライスし
て２枚のシートを得た。しかる後、該シートをパフ別に
かけて立毛を形成させ立毛シートとした後、分散染料を
用いて１２０℃、６０分間液流染色し、厚さ０．６９Ｍ
１、目付１８１Ｑ／ｉ’、見掛密度０．２６２ｇ１０＋
ｆのスェード調人工皮革を得た。This place PI! The polyurethane was coagulated by introducing it into water at 4130°C, and then polyvinyl alcohol and dimethylformamide were removed by washing in hot water. The weight of polyurethane obtained by these treatments is 3% per 100 parts of fiber.
It was 0 copies. Next, this sheet was sliced in the plane direction to obtain two sheets. After that, the sheet was puffed separately to form a nap to form a nap sheet, and then jet dyed using a disperse dye at 120°C for 60 minutes to a thickness of 0.69M.
1. Fabric weight 181Q/i', apparent density 0.262g10+
A suede-like artificial leather of f was obtained.
１ｑられた人工皮革は従来のものに比べてきわめて柔軟
でドレープ性に富み、しかも優れた機械的性能を右する
ものでｄうり、薄地衣料素材として適するものであった
。The manufactured artificial leather was extremely flexible and drapable compared to conventional leather, and also had excellent mechanical performance, making it suitable as a material for thin clothing.
実施例２
島成分がポリエチレンテレフタレート、海成分がポリス
チレンの成分比５０１５０、太さ３．０デニール、島数
２２３本１． 、− 井カット長５１ ｍｍＳ捲縮
数１５〜１８山／インチの筒分子配列体繊キ（［からな
る原綿を用いてカード、クロスラッパーを通して日付６
２０ｇ／Ｔｒ１１のウェッブを作成した。該ウェッブに
針密度３５００本７／ｄの二一ドルパンヂを行ない目イ
づ５９５０ ／ ｒｎ２、見掛密度０．２３３Ｑ／ａ（
の不械布繊耗シートとし、次いでオリフィスの径０．２
０画、ビッヂ１゜ＯＩＴ１ｍ１水圧１００ｋｉ／１ｎｉ
ｉｉ：動幅１０面、揺動サイクル３回／秒、処理速度２
５ｃｍ／分のウォータージェットパンチ処理を不織布繊
組シートの表裏８１回行なった。この時の不織布繊組シ
ートの目イづは５９５ｇ／ｙｎ’、見掛密度は０．２８
４であった。このシートを９０℃の熱水中に３分間浸漬
して収縮させた。この時の面積収縮率は２３．０％であ
った。このシートをポリビニルアルコールの１２％水溶
液に浸１責した後、マングルで絞る操作に行ない、楳ｔ
−ｔｔ ｉ ｏ ｏ部に対してポリビニルアルコール３
８．６部付看させた。次いでトリクロルエチレン中にＳ
潰し、海成分を除去した後にポリウレタンの１２％ジメ
ヂルホルムアミド溶液に浸漬した後マングルで絞ってポ
リウレタン溶液を何Ｌ５Ｌ、た。その後、該シートを２
５％ジメチルホルムアミド水溶液からなる凝固浴中へ３
分間浸漬した後、凝固浴から取出し、該シートの上面か
ら２５％ジメチルホルムアミド水溶液を噴出流体として
用いる高速流体処理を行ない、続いて下面から同じ処理
を行なった。この高速流体処理条件はオリフィス径０．
２５ｍｍφ、オリフィスピッチ２゜５＋１Ｙ１１％水圧
１０（１１１０（、噴出流体速度１４１ｍ／秒、揺動幅
１０飾、揺動サイクル３回／秒、処理速度２５ Ｃ１１
ｌ／分であり、この時の噴出流体はシートを貫通した。Example 2 The island component is polyethylene terephthalate, the sea component is polystyrene, the component ratio is 50150, the thickness is 3.0 denier, and the number of islands is 223.1. , - Cutting length 51 mmS crimping number 15-18 threads/inch Cylindrical molecular array fiber ([Created using raw cotton, card, cross wrapper, date 6
A web of 20 g/Tr11 was prepared. The web was subjected to 21 dollar punching with a needle density of 3,500 needles 7/d to give an eye count of 5,950/rn2 and an apparent density of 0.233Q/a (
A non-machine abrasion sheet with an orifice diameter of 0.2
0 stroke, bit 1゜OIT1m1 water pressure 100ki/1ni
ii: Dynamic width 10 planes, rocking cycle 3 times/sec, processing speed 2
Water jet punching at a rate of 5 cm/min was performed 81 times on both sides of the nonwoven fabric sheet. At this time, the mesh size of the nonwoven fabric sheet was 595 g/yn', and the apparent density was 0.28.
It was 4. This sheet was immersed in hot water at 90° C. for 3 minutes to shrink. The area shrinkage rate at this time was 23.0%. After soaking this sheet in a 12% aqueous solution of polyvinyl alcohol, it was squeezed with a mangle, and then
-tt i o 3 parts of polyvinyl alcohol
8. I was given 6th copy. Then S in trichlorethylene
After crushing and removing the sea component, it was immersed in a 12% polyurethane dimedylformamide solution, and then squeezed with a mangle to obtain several liters of polyurethane solution. After that, the sheet is
3 into a coagulation bath consisting of a 5% dimethylformamide aqueous solution.
After being immersed for a minute, the sheet was removed from the coagulation bath and subjected to a high-speed fluid treatment using a 25% dimethylformamide aqueous solution as a jetting fluid from the top surface, followed by the same treatment from the bottom surface. This high-speed fluid processing condition is based on an orifice diameter of 0.
25mmφ, orifice pitch 2゜5+1Y11% water pressure 10 (1110), jetting fluid velocity 141 m/sec, swing width 10 ornaments, swing cycle 3 times/sec, processing speed 25 C11
l/min, and the ejected fluid at this time penetrated the sheet.
この処理後３０℃の水中に導いてポリウレタンを凝固し
、次いで熱水中でポリビニルアルコール及びジメチル２
４〜ルムアミドを洗浄し除去した。これらの処理による
ポリウレタンの何者ｍはｌＪ［１００ｔ！ｌ１３に対し
て２６部であった。After this treatment, the polyurethane was introduced into water at 30°C to coagulate, and then polyvinyl alcohol and dimethyl 2
4 - Lumamide was washed and removed. The mass of polyurethane obtained by these treatments is lJ[100t! It was 26 parts to l13.
次いでこのシートを面方向にスライスして２枚のシート
を得た。しかる後、該シートをパフ機にか（プて立毛を
形成させ立毛シートとした後、分子ｌｌ染料を用いて１
２０℃、６０分間液流染色し、厚さ０．４９ｍ、目付１
８０Ｑ／ｌｎ２、見掛密度０．３６７ｑ１０＋ｔのスェ
ード調人工皮革を得た。Next, this sheet was sliced in the plane direction to obtain two sheets. After that, the sheet was put in a puff machine (to form a nap to form a nap sheet), and then 1
Jet dyed at 20℃ for 60 minutes, thickness 0.49m, basis weight 1
A suede-like artificial leather having an apparent density of 80Q/ln2 and an apparent density of 0.367q10+t was obtained.
得られた人工皮革は従来のものに比べて薄く、実施例１
と同様きわめてドレープ性良好なものであった。The obtained artificial leather was thinner than conventional leather, and was similar to Example 1.
Similarly, the drapability was extremely good.
実施例３
実施例２で１ｑられたスェード町人工皮革を基材として
用い、一方シボ模様を有する離型紙上に顔料を含有した
５％未反応ポリウレタン調合液をコレタン調合液をコー
トし、約２０μの乾式塗膜を積層して、前者を銀面層と
し、後者を基材と接着させるための接着層とする積層塗
膜を形成させた。Example 3 Using the Suede Town artificial leather prepared in Example 2 as a base material, a 5% unreacted polyurethane mixture containing a pigment was coated on a release paper having a grain pattern, and a corethane mixture was coated on a release paper having a grain pattern to form a layer of approximately 20 μm. The dry coating films were laminated to form a laminated coating film in which the former was used as a silver surface layer and the latter was used as an adhesive layer for adhering to the base material.
かかるｍＦｊｌＱ膜と基材をクリアランスＱ、２ｍｍ。The mFjlQ film and the substrate have a clearance Q of 2 mm.
温度約７０℃の熱ロールに通して貼合せ、しかる後、４
０℃、１日間熟成して接ｊ４ＦＪのポリウレタンを架橋
反応せしめた。次いで離型紙を’ＡＭして根付人工皮革
をつくった。、得られた根付人工皮革は従来の方法によ
るものより、（々めて柔軟であり、ドレープ性に富み、
表面に緻密なシボ及び折れしわを有する天然皮革に酷似
し拳ものであった。Pass it through a hot roll at a temperature of about 70°C and paste it, then 4
It was aged at 0° C. for 1 day to cause a crosslinking reaction in the polyurethane of contact j4FJ. Next, the release paper was subjected to AM to produce netsuke artificial leather. The resulting netsuke artificial leather is much more flexible and drapeable than those made using conventional methods.
It closely resembled natural leather with fine grains and creases on the surface.
比較例１
実施例１と同じ海成分除去シートを用いて、ポリウレタ
ンの１０％ジメチルホルムアミド溶液中に浸漬した後マ
ングルでニップしてポリウレタン溶液を付与した。この
後該シートを水中に導いてポリウレタンを凝固し、次い
で熱水中でポリビニルアルコール及びジメチルホルムア
ミドを洗浄し除去した。これらの処理によるポリウレタ
ンの付＠ｆｎ＋ｔｍＨ１００部に対して３１部であった
。次いで該シートを面方向にスライスして２枚のシート
とした。しかる後、該シー１〜をパフ機にかけて立毛を
形成させ、次いで分散％？Ｅを用いて１２０℃、６０分
間液流染色し、厚さ０．６７画、目付１８５ｇ／が、見
掛密度０．２７６ｇ／ｆｆｌのスェード調人工皮革を１
９だ。Comparative Example 1 Using the same sea component removal sheet as in Example 1, the sheet was immersed in a 10% polyurethane dimethylformamide solution and then nipped with a mangle to apply the polyurethane solution. Thereafter, the sheet was introduced into water to coagulate the polyurethane, and then the polyvinyl alcohol and dimethylformamide were removed by washing in hot water. The amount of polyurethane added by these treatments was 31 parts per 100 parts of @fn+tmH. The sheet was then sliced in the plane direction into two sheets. After that, the seams 1 to 1 are applied to a puff machine to form raised fluff, and then the dispersion percentage is 100%. The suede-like artificial leather with a thickness of 0.67 strokes, a basis weight of 185 g/, and an apparent density of 0.276 g/ffl was dyed using E at 120°C for 60 minutes.
It's 9.
ｉｑられた人工皮革は実施例に比べて明らかに反光性の
ある硬い風合であり、薄地衣料用としては適さないもの
であった。The iq-treated artificial leather had a stiff texture with clear anti-light properties compared to the examples, and was unsuitable for use in thin clothing.
次に本発明に係る実施例１、実施例２および比較例１の
物性を第１表に示した。Next, the physical properties of Example 1, Example 2 and Comparative Example 1 according to the present invention are shown in Table 1.
第１表 〔発明の効果〕 本発明によれば次のような効果が得られる。Table 1 〔Effect of the invention〕 According to the present invention, the following effects can be obtained.
（１）柔軟でドレープ性に富んだ人工皮革が得られる。(1) Artificial leather that is flexible and has excellent drapability can be obtained.
（２＞ ＩＩ械的性ｆ１ヒの優れた人工皮革が１ｑられ
る。(2> II 1q of artificial leather with excellent mechanical properties f1) is produced.
（３）毛羽落ちの少ない立上タイプ人１皮７ｆＩがＩＪ
られる。(3) Stand-up type human 1 skin 7fI with little shedding is IJ
It will be done.
（４）高能率かつ、均一な凝固ができる。(4) Highly efficient and uniform coagulation is possible.
（５）加工上の寸法保持性が良好となる。(5) Good dimensional retention during processing.
（６）立毛加工が容易となる。(6) The raising process becomes easy.
Claims (1)
トの製造方法において、繊維シートに付与された高分子
弾性体液が完全凝固するまでに高速流体処理を施すこと
を特徴とする人工皮革シートの製造方法。A method for manufacturing an artificial leather sheet by adding a polymeric elastic body to a fiber sheet, characterized in that high-speed fluid treatment is performed until the polymeric elastic body fluid applied to the fiber sheet is completely solidified. Production method.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15133784A JPS6134286A (en) | 1984-07-23 | 1984-07-23 | Production of artificial leather sheet |
| US06/755,072 US4741075A (en) | 1984-07-23 | 1985-07-15 | Composite sheet and method of producing same |
| AT85305113T ATE84330T1 (en) | 1984-07-23 | 1985-07-18 | ARTIFICIAL LEATHER AND ITS PRODUCTION PROCESS. |
| DE19853586958 DE3586958T2 (en) | 1984-07-23 | 1985-07-18 | ARTIFICIAL LEATHER AND METHOD FOR THE PRODUCTION THEREOF. |
| EP19850305113 EP0176181B1 (en) | 1984-07-23 | 1985-07-18 | Artificial leather and method for producing same |
| CA000487192A CA1240885A (en) | 1984-07-23 | 1985-07-22 | Composite sheet and method of producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15133784A JPS6134286A (en) | 1984-07-23 | 1984-07-23 | Production of artificial leather sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6134286A true JPS6134286A (en) | 1986-02-18 |
Family
ID=15516368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15133784A Pending JPS6134286A (en) | 1984-07-23 | 1984-07-23 | Production of artificial leather sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6134286A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01221002A (en) * | 1988-02-29 | 1989-09-04 | Nec Corp | Microwave integrated circuit |
| JPH05179547A (en) * | 1991-09-20 | 1993-07-20 | Chiyoda Kk | Wiping cloth |
| JP2002180378A (en) * | 2000-12-12 | 2002-06-26 | Kuraray Co Ltd | Method for producing fabric having coated layer composed of polymer elastomer |
| ES2265777A1 (en) * | 2005-08-01 | 2007-02-16 | Industrias Tapla, S.L. | Fiber covering material for cladding parts with a superimposed layer (1) based on polypropylene, polyester, polyethylene foam or polyvinyl acetate useful for cladding inner components of automobiles |
| EP2006439A2 (en) | 2006-02-28 | 2008-12-24 | Kuraray Co., Ltd. | Artificial leather and method for producing the same |
| KR20190002818A (en) * | 2017-06-30 | 2019-01-09 | 코오롱인더스트리 주식회사 | Manufacturing method of artificial leather with improved appearance property |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5616222A (en) * | 1979-07-19 | 1981-02-17 | Fujitsu Ltd | Error report system for input and output control unit |
-
1984
- 1984-07-23 JP JP15133784A patent/JPS6134286A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5616222A (en) * | 1979-07-19 | 1981-02-17 | Fujitsu Ltd | Error report system for input and output control unit |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01221002A (en) * | 1988-02-29 | 1989-09-04 | Nec Corp | Microwave integrated circuit |
| JPH05179547A (en) * | 1991-09-20 | 1993-07-20 | Chiyoda Kk | Wiping cloth |
| JP2002180378A (en) * | 2000-12-12 | 2002-06-26 | Kuraray Co Ltd | Method for producing fabric having coated layer composed of polymer elastomer |
| JP4610725B2 (en) * | 2000-12-12 | 2011-01-12 | 株式会社クラレ | Method for producing fabric having coat layer made of polymer elastic body |
| ES2265777A1 (en) * | 2005-08-01 | 2007-02-16 | Industrias Tapla, S.L. | Fiber covering material for cladding parts with a superimposed layer (1) based on polypropylene, polyester, polyethylene foam or polyvinyl acetate useful for cladding inner components of automobiles |
| EP2006439A2 (en) | 2006-02-28 | 2008-12-24 | Kuraray Co., Ltd. | Artificial leather and method for producing the same |
| KR20190002818A (en) * | 2017-06-30 | 2019-01-09 | 코오롱인더스트리 주식회사 | Manufacturing method of artificial leather with improved appearance property |
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