JPH06330474A - Leathery sheetlike material excellent in flexibility and production thereof - Google Patents

Leathery sheetlike material excellent in flexibility and production thereof

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Publication number
JPH06330474A
JPH06330474A JP5052694A JP5052694A JPH06330474A JP H06330474 A JPH06330474 A JP H06330474A JP 5052694 A JP5052694 A JP 5052694A JP 5052694 A JP5052694 A JP 5052694A JP H06330474 A JPH06330474 A JP H06330474A
Authority
JP
Japan
Prior art keywords
coating layer
layer
elastic polymer
sheet
fine particles
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.)
Granted
Application number
JP5052694A
Other languages
Japanese (ja)
Other versions
JP3142103B2 (en
Inventor
Yutaka Komura
豊 小村
Kazuto Akamata
一人 赤股
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP5052694A priority Critical patent/JP3142103B2/en
Publication of JPH06330474A publication Critical patent/JPH06330474A/en
Application granted granted Critical
Publication of JP3142103B2 publication Critical patent/JP3142103B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Landscapes

  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)

Abstract

PURPOSE:To provide a leathery sheetlike material, having flexibility and drapeability suitable for uses of thin high-class grained clothes and various gloves, a moisture permeability as high as >=4000g/m<2>.24hr and smooth appearance with high-class feeling close to that of natural leather. CONSTITUTION:The leathery sheetlike material has a coating layer of an elastic polymer on the surface of a substrate layer containing the elastic polymer in a fibrous assembly and is excellent in flexibility. This leathery sheetlike material is characterizing by integrating the coating layer of the elastic polymer with the substrate layer and constituting the coating layer from two layers of a wet porous intermediate coating layer having open cells of 1-30mum maximum pore diameter observed in the cross section and 10-40mum thickness and a dry porous surface coating layer, obtained by extracting and removing fine particles and having open cells of substantial <=20mum maximum pore diameter observed in the cross section and 20-80mum thickness. Both the layers contain a softening agent.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、銀付き衣料、各種手
袋、ソフトなスポーツシューズ用途等に最適な柔軟性、
ドレ−プ性、透湿性に優れ、かつ天然皮革に類似したス
ム−スで高級感のある外観を合せ持つ皮革様シ−ト状物
及びその製造方法に関するものである。
BACKGROUND OF THE INVENTION The present invention is suitable for clothing with silver, various gloves, soft sports shoes, etc.
The present invention relates to a leather-like sheet having excellent drapability and moisture permeability and having a smooth and high-quality appearance similar to natural leather, and a method for producing the same.

【0002】[0002]

【従来の技術】従来、柔軟性、透湿性に優れた銀付調皮
革様シ−ト状物としては、多孔質弾性重合体を含む繊維
質基体層表面に弾性重合体を主体とした重合体の多孔質
被覆層や無孔質被覆層を積層したもの、あるいは多孔質
被覆層表面にさらに無孔質被覆層を積層したものが知ら
れている。多孔質被覆層を得る方法としては、弾性重合
体の溶液を該弾性重合体の非溶剤で処理して多孔質に凝
固させる湿式凝固法、弾性重合体溶液に塩類やでんぷ
ん、ゼラチンなどの易抽出性の微粒子を混合した組成液
を塗布乾燥した後、あるいは弾性重合体に上記易抽出性
の微粒子を混練しシート状とした後、該微粒子を抽出除
去して多孔質構造とする方法、乾式発泡による方法、な
どが知られている。また、湿式微多孔層の表面にゼラチ
ンやでんぷんなどの水溶性天然高分子の微粉末を混合し
たポリウレタン樹脂層を形成し水溶性微粉末を溶解除去
して多孔質被覆層とすることが、特開平2−91279
号公報、特開平2−169777号公報、特開平2−3
07987号公報に提案されている。
2. Description of the Related Art Conventionally, as a leather-like sheet with silver having excellent flexibility and moisture permeability, a polymer mainly composed of an elastic polymer on the surface of a fibrous substrate layer containing a porous elastic polymer. It is known that a porous coating layer or a non-porous coating layer is laminated, or a non-porous coating layer is further laminated on the surface of the porous coating layer. As a method for obtaining a porous coating layer, a wet coagulation method in which a solution of an elastic polymer is treated with a non-solvent of the elastic polymer to coagulate it into a porous state, and salts, starch, gelatin, etc. are easily extracted into the elastic polymer solution. After coating and drying a composition liquid containing water-soluble fine particles, or kneading the elastic polymer with the easily extractable fine particles to form a sheet, and then extracting and removing the fine particles to form a porous structure, dry foaming Method, etc. are known. In addition, it is possible to form a polyurethane resin layer by mixing fine powder of water-soluble natural polymer such as gelatin or starch on the surface of the wet microporous layer, and dissolve and remove the water-soluble fine powder to form a porous coating layer. Kaihei 2-91279
Japanese Patent Application Laid-Open No. 2-169777, Japanese Patent Application Laid-Open No. 2-3
It is proposed in Japanese Patent Publication No. 07987.

【0003】[0003]

【発明が解決しようとする課題】従来提案されている柔
軟性、透湿性を特徴とする皮革様シ−ト状物は各種ある
がこれらはいずれも優れた柔軟性、ドレ−プ性、透湿
性、表面の高級感を合わせて必要とする高級銀付き衣
料、各種手袋用途には不十分であった。即ち、表面層と
して多孔質湿式膜を付与する方法は湿式膜だけで表面の
平滑性を得ようとすれば厚い膜を必要とし風合いが悪く
なり、また多孔質湿式膜の上に仕上げ層として非多孔質
の乾式膜を付与することで表面層が硬くなり基体層との
バランスが崩れ一体感のない物となる傾向にあった。一
方乾式造面法等で無孔質膜や多孔質膜を付与する方法は
比較的薄膜で造面可能だが表面の高級感に欠け、また、
衣料、各種手袋用途には柔軟性、ドレ−プ性が不足し、
透湿性も不十分であった。また、前記湿式微多孔層の表
面に水溶性天然高分子の微粉末を混合したポリウレタン
樹脂層を形成し水溶性微粉末を溶解除去して多孔質被覆
層とする方法でも、湿式微多孔層の厚みが厚く、しかも
水溶性天然高分子微粉末の粒径が大きいため、除去して
得られる多孔質層の孔径が大きく、薄地の衣料、各種手
袋用途にはやはり柔軟性、ドレ−プ性が不足し、透湿性
も不十分であった。本発明は、上記問題点を解決し、優
れた柔軟性、ドレ−プ性を有し、4000g/m2・24h
以上の高い透湿性があり、かつ天然皮革に類似したスム
−スで高級感のある外観を合せ持つ皮革様シ−ト状物及
びその製造方法を提供することにある。
There are various kinds of leather-like sheet materials which have been proposed so far and are characterized by flexibility and moisture permeability, and all of them have excellent flexibility, drape property and moisture permeability. However, it was inadequate for high-grade silver-coated clothing, which requires a high-quality surface, and various gloves. That is, the method of applying a porous wet film as the surface layer requires a thick film to obtain smoothness of the surface only with the wet film, and the texture becomes poor, and a non-finishing layer is formed on the porous wet film as a finishing layer. By providing a porous dry film, the surface layer was hardened and the balance with the substrate layer was lost, and the product tended to have no sense of unity. On the other hand, a method of applying a non-porous film or a porous film by a dry surface forming method or the like can form a surface with a relatively thin film, but lacks a high-class surface feeling.
Lack of flexibility and drapeability for clothing and various gloves,
The moisture permeability was also insufficient. In addition, a method of forming a polyurethane resin layer in which a fine powder of a water-soluble natural polymer is mixed on the surface of the wet microporous layer, and dissolving and removing the water-soluble fine powder to form a porous coating layer also produces a wet microporous layer. Since the water-soluble natural polymer fine powder has a large thickness and the particle size of the water-soluble natural polymer fine powder is large, the pore size of the porous layer obtained by removal is large, and it is still flexible and drapeable for thin clothing and various gloves. It lacked and had insufficient moisture permeability. The present invention solves the above problems and has excellent flexibility and drapeability, and 4000 g / m 2 · 24h
It is an object of the present invention to provide a leather-like sheet having a high moisture permeability and a smooth, high-quality appearance similar to natural leather, and a method for producing the same.

【0004】[0004]

【課題を解決するための手段】本発明者らは、表面層の
構成に着目し、鋭意検討を行った結果、基体層と一体化
した表面多孔質薄膜の上に特定粒子を抽出して得られた
多孔質乾式膜を作ることにより、上記特徴を合せ持つ皮
革様シ−ト状物が出来ることを見出だした。即ち、本発
明は、繊維集合体に弾性重合体を含有した基体層の表面
に弾性重合体の被覆層を有するシ−ト状物において、該
被覆層が基体層と一体化され、かつ断面で観察した最大
孔径1〜30μmの連続した気孔を有する厚さ10〜4
0μmの湿式多孔質中間被覆層と、微粒子を抽出除去し
て得られ断面で観察した最大孔径が実質的に20μm以
下の気孔を有する厚さ20〜100μmの乾式多孔質表
面被覆層の2層から構成され、かつ両層とも柔軟剤を含
有することを特徴とする柔軟性に優れた皮革様シ−ト状
物であり、その製造方法としては、(a) シート状の繊維
集合体を形成する工程、(b) 該繊維集合体に弾性重合体
の組成液を含浸し凝固して繊維集合体に弾性重合体を含
有した基体層を形成する工程、(c) 該繊維集合体の表面
に弾性重合体の組成液を塗布し湿式凝固して基体層と一
体化された厚さ10〜40μmで断面で観察した最大孔
径1〜30μmの気孔を有する湿式多孔質中間被覆層を
形成する工程、(d) 離型紙上に弾性重合体の溶液に熱水
抽出性微粒子を混入した弾性重合体組成液を塗布し該湿
式多孔質中間被覆層上に貼合せ乾燥した後離型紙を剥離
し乾式膜を形成する工程、(e) 該乾式膜から該熱水抽出
性微粒子を熱水抽出することにより断面で観察した最大
孔径0.5〜20μmの連続した気孔を有する厚さ20
〜100μmの乾式多孔質表面被覆層に変性する工程、
(f) 少なくとも湿式多孔質中間被覆層と乾式多孔質表面
被覆層に柔軟剤を付与する工程、を組み合わせることに
より柔軟性に優れた皮革様シ−ト状物を製造するもので
ある。
Means for Solving the Problems The present inventors focused their attention on the constitution of the surface layer, and as a result of diligent studies, as a result, extracted specific particles on the surface porous thin film integrated with the substrate layer. It has been found that a leather-like sheet having the above-mentioned characteristics can be produced by making the porous dry film. That is, the present invention provides a sheet-like material having a coating layer of an elastic polymer on the surface of a substrate layer containing an elastic polymer in a fiber assembly, the coating layer being integrated with the substrate layer and having a cross section. Observed maximum pore diameter 1 to 30 μm and thickness 10 to 4 having continuous pores
From a dry porous surface coating layer having a thickness of 20 to 100 μm and a wet porous intermediate coating layer having a thickness of 0 μm, and pores obtained by extracting and removing fine particles and having a maximum pore size of 20 μm or less observed in a cross section. A leather-like sheet having excellent flexibility, which is characterized by containing a softening agent in both layers, and as a method for producing the same, (a) forming a sheet-shaped fiber aggregate. Step (b) a step of impregnating the fiber assembly with a composition liquid of an elastic polymer and solidifying the composition to form a base layer containing the elastic polymer in the fiber assembly, (c) elasticity on the surface of the fiber assembly Forming a wet porous intermediate coating layer having a thickness of 10 to 40 μm integrated with a substrate layer and having pores with a maximum pore diameter of 1 to 30 μm, which is integrated with a substrate layer by applying a composition liquid of a polymer, d) On the release paper, an elastic polymer solution mixed with hot water extractable fine particles is used. A step of applying a polymer composition liquid, laminating on the wet porous intermediate coating layer and drying, and then peeling off the release paper to form a dry film, (e) extracting the hot water extractable fine particles from the dry film with hot water And a thickness of 20 having continuous pores having a maximum pore diameter of 0.5 to 20 μm observed in a cross section.
Denaturing to a dry porous surface coating layer of -100 μm,
(f) A leather-like sheet having excellent flexibility is manufactured by combining at least the step of applying a softening agent to the wet porous intermediate coating layer and the dry porous surface coating layer.

【0005】本発明の基体層を構成する繊維集合体とし
ては、長繊維や短繊維からなる織物、編物、不織布等の
シート状物を用いることが出来るが、織編物の場合は表
面の平滑性の点から少なくとも一面を起毛した物である
ことが好ましい。基体層の厚さの調節の容易さ、皮革に
類似した柔軟な風合い等の点で繊維集合体として不織布
を用いることが特に好ましく、さらに不織布には補強用
等の目的で内部又は一面に織編物を積層一体化した物で
あってもよい。
As the fiber assembly constituting the base layer of the present invention, sheet-like materials such as woven fabrics, knitted fabrics and non-woven fabrics made of long fibers and short fibers can be used. From the above point, it is preferable that at least one surface is raised. It is particularly preferable to use a non-woven fabric as a fiber assembly in terms of the ease of adjusting the thickness of the base layer and the soft texture similar to leather, and the non-woven fabric is woven or knitted on the inside or one side for the purpose of reinforcement. It may be a laminated and integrated product.

【0006】該繊維集合体を構成する繊維としては、通
常の繊維、例えば、ポリエステル、ポリアミド、ポリア
クリロニトリル、ポリオレフィン、ポリビニ−ルアルコ
−ルなどの合成繊維、再生セルロ−ズなどの化学繊維、
天然繊維、あるいは特殊形態の繊維、例えば、ポリエス
テル、ポリアミドなどの極細繊維や、溶剤や分解剤など
に対する溶解性や分解性の異なる2種以上の樹脂からな
る多成分繊維の少なくとも1成分を溶解や分解除去する
ことにより変成された極細繊維束状繊維や特殊多孔繊維
などから用途により適宜選ぶことができる。得られるシ
ート状物の柔軟性やドレ−プ性の点から、ポリエステル
やポリアミドなど、特にポリアミドの単繊維繊度が0.
1〜0.0001デニールの極細繊維あるいは極細繊維
束状繊維が好ましい。また、繊維強度に影響を与えない
範囲で繊維の延伸条件を下げることにより、よりソフト
なシ−ト状物を得ることができる。
The fibers constituting the fiber assembly are ordinary fibers, for example, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, polyvinyl alcohol, and chemical fibers such as recycled cellulose,
At least one component of a natural fiber or a fiber of a special form, for example, an ultrafine fiber such as polyester or polyamide, or a multi-component fiber composed of two or more kinds of resins having different solubility or degradability with respect to a solvent or a degrading agent is dissolved or It can be appropriately selected from ultrafine fiber bundle-like fibers modified by decomposition and removal, special porous fibers and the like depending on the application. From the viewpoints of flexibility and drapeability of the obtained sheet-like material, polyester, polyamide, etc., particularly polyamide, has a single fiber fineness of 0.
Ultrafine fibers or ultrafine fiber bundle fibers having a denier of 1 to 0.0001 are preferable. Further, a softer sheet-like material can be obtained by lowering the fiber drawing conditions within a range that does not affect the fiber strength.

【0007】これらの繊維はニ−ドルパンチや高速流体
流により絡合処理された不織布、立毛編織布、不織布と
編織布の積層布などの布帛とする。なお、基体層を構成
する繊維集合体として極細繊維束状繊維や特殊多孔繊維
を用いる場合は、変成後の繊維を用いて繊維集合体を形
成することが困難であるため、変成前の多成分繊維を用
いて繊維集合体を形成し、弾性重合体を含浸後に多成分
繊維を極細繊維束状繊維や特殊多孔繊維に変成すること
が好ましい。繊維集合体の重量は、特に限定される物で
はなく、目的とする最終的な用途分野に応じて適宜選択
すればよく、通常は100〜1000g/m2の範囲から
選ばれる。繊維集合体が不織布の場合には、弾性重合体
の含浸処理などの工程通過性の点から200g/m2以上
であることが好ましく、衣料用などに使用する薄地の物
を製造するときには必要とする重量の約2倍の重量の繊
維集合体に弾性重合体を含浸し、両面に湿式多孔質中間
被覆層を形成した後バンドナイフなどにより厚さ方向を
2分割することにより湿式多孔質中間被覆層が積層され
た基体層を1度に2枚製造することもできる。繊維集合
体は、重合体溶液の含浸処理に先立って、必要に応じて
熱プレスなどの従来公知の方法により表面の平滑化処理
を行う。繊維集合体を構成する繊維がポリエチレンを海
成分とし、ポリエステルやポリアミドを極細の島成分と
する多成分繊維である場合は、熱プレスにより海成分の
ポリエチレンを溶着させることにより極めて表面平滑性
に優れた繊維集合体とすることが出来るので特に好まし
い。繊維集合体を構成する繊維が1成分を溶解除去して
極細繊維に変成することの出来る多成分繊維でない場合
には、含浸する弾性重合体が繊維に固着して風合いが硬
くなることを防止するために、弾性重合体の含浸に先立
ってポリビニルアルコールなどの仮充填物質で繊維表面
を覆っておくことが好ましい。
These fibers are used as a cloth such as a nonwoven fabric which has been entangled by a needle punch or a high-speed fluid flow, a napped knitted woven fabric, and a laminated fabric of the nonwoven fabric and the knitted fabric. When ultrafine fiber bundle fibers or special porous fibers are used as the fiber assembly constituting the base layer, it is difficult to form the fiber assembly using the modified fiber, and thus the multi-component fiber before modification is used. It is preferable that a fiber aggregate is formed by using the fibers, and after the elastic polymer is impregnated, the multi-component fibers are transformed into ultrafine fiber bundle fibers or special porous fibers. The weight of the fiber assembly is not particularly limited and may be appropriately selected according to the intended final field of use, and is usually selected from the range of 100 to 1000 g / m 2 . When the fiber assembly is a non-woven fabric, it is preferably 200 g / m 2 or more from the viewpoint of processability such as the impregnation treatment of the elastic polymer, which is necessary when manufacturing a thin material used for clothing and the like. A wet porous intermediate coating is prepared by impregnating a fiber aggregate having a weight about twice that of the elastic polymer with an elastic polymer, forming a wet porous intermediate coating layer on both surfaces, and then dividing the thickness direction into two by a band knife or the like. It is also possible to produce two substrate layers in which the layers are laminated at one time. Prior to the impregnation treatment with the polymer solution, the fiber assembly is, if necessary, subjected to surface smoothing treatment by a conventionally known method such as hot pressing. When the fibers that make up the fiber assembly are multi-component fibers with polyethylene as the sea component and polyester or polyamide as the ultrafine island component, the surface of the sea component is extremely smooth by welding the polyethylene as the sea component by hot pressing. It is particularly preferable because it can be made into a fiber aggregate. When the fiber constituting the fiber assembly is not a multi-component fiber capable of dissolving and removing one component to be transformed into an ultrafine fiber, it prevents the impregnated elastic polymer from sticking to the fiber and hardening the texture. Therefore, it is preferable to cover the fiber surface with a temporary filling substance such as polyvinyl alcohol before the impregnation with the elastic polymer.

【0008】繊維集合体に含浸する弾性重合体、又はそ
の表面に薄膜で被覆層として付与する弾性重合体は、ポ
リウレタン、アクリル系重合体、アクリロニトリル・ブ
タジエン共重合体、スチレン・ブタジエン共重合体など
の弾性重合体の群から選ばれた少なくとも1種類の弾性
重合体を主体とした重合体を用いることができる。風合
い、耐久性等の点から特にポリウレタンが好ましい。ポ
リウレタンとしては、平均分子量500〜2500のポ
リマ−ジオ−ル、例えば、ポリエステルジオ−ル、ポリ
エ−テルジオ−ル、ポリエステル・エ−テルジオ−ル、
ポリカプロラクトンジオ−ル、ポリカ−ボネ−トジオ−
ルなどの中から選ばれた少なくとも1種類のジオ−ル
と、有機ポリイソシアネ−ト、例えば、芳香族ジイソシ
アネ−ト、芳香族トリイソシアネ−ト、脂環族ジイソシ
アネ−ト、環状基を有する脂肪族ジイソシアネ−ト、ト
リフェニルメタン4,4’,4”−トリイソシアネ−ト
などの群から選ばれた少なくとも1種類の有機ポリイソ
シアネ−トと、活性水素原子を少なくとも2個有する低
分子化合物を鎖伸長剤として反応させて得た熱可塑性ポ
リウレタンである。これらのポリウレタンの組成は該皮
革様シ−ト状物の指向する用途分野に応じて、風合い、
耐劣化性、耐黄変性、染色性等の各種物性を満足するも
のの中から適宜選ぶことができる。
The elastic polymer impregnated into the fiber assembly or the elastic polymer provided as a thin film coating layer on the surface of the fiber assembly includes polyurethane, acrylic polymer, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer and the like. It is possible to use a polymer mainly composed of at least one kind of elastic polymer selected from the group of elastic polymers mentioned above. Polyurethane is particularly preferable in terms of texture and durability. As the polyurethane, a polymer diol having an average molecular weight of 500 to 2,500, for example, polyester diol, polyester diol, polyester ether diol,
Polycaprolactone diol, Polycarbonate diodiol
And at least one type of diole selected from the group consisting of aromatic diisocyanate, aromatic triisocyanate, alicyclic diisocyanate, and aliphatic diisocyanate having a cyclic group. -, Triphenylmethane 4,4 ', 4 "-triisocyanate, etc., and at least one organic polyisocyanate selected from the group, and a low molecular weight compound having at least two active hydrogen atoms as a chain extender. It is a thermoplastic polyurethane obtained by reacting the composition of these polyurethanes, depending on the field of application for which the leather-like sheet is intended,
It can be appropriately selected from those satisfying various physical properties such as deterioration resistance, yellowing resistance, and dyeability.

【0009】弾性重合体を主体とした重合体は、溶剤に
溶解し、必要に応じて従来公知の凝固調節剤、着色剤な
どを添加して含浸用の組成液とする。含浸用の組成液は
繊維集合体に含浸して重合体の非溶剤中に浸漬して多孔
質に凝固させる。繊維集合体に含浸した弾性重合体の凝
固法としては、湿式法の他に水蒸気凝固などの方法も採
用することが出来る。乾式法による凝固は一般に風合い
が硬くなるため本発明では用いられない。繊維集合体が
少なくとも1成分を除去することにより極細繊維束状繊
維や特殊多孔繊維などに変成することのできる多成分繊
維を含む場合には、重合体を含浸、凝固した後適当な溶
剤あるいは分解剤などで処理して多成分繊維を極細繊維
束状繊維や特殊多孔繊維などに変成する。
A polymer mainly composed of an elastic polymer is dissolved in a solvent, and if necessary, a conventionally known coagulation regulator, colorant and the like are added to prepare a composition liquid for impregnation. The composition liquid for impregnation is impregnated into the fiber aggregate and immersed in a non-solvent of the polymer to solidify it into a porous structure. As a coagulation method for the elastic polymer impregnated in the fiber aggregate, a method such as steam coagulation can be adopted in addition to the wet method. Coagulation by the dry method is generally not used in the present invention because the texture becomes hard. When the fiber assembly contains multi-component fibers that can be transformed into ultrafine fiber bundle fibers or special porous fibers by removing at least one component, after impregnating and coagulating the polymer, a suitable solvent or decomposition is applied. It is treated with agents to transform multi-component fibers into ultrafine fiber bundle fibers and special porous fibers.

【0010】基体層と一体化された中間被覆層(スキン
層)は表面平滑性、柔軟性、透湿性、良好な折れシボ感
を得るために不可欠の層である。即ち、基体層と乾式多
孔質表面被覆層の中間に位置して前記特徴を出すと共に
皮革様シ−トとして一体感のある好ましい風合いを作り
出す役目を持っている。この中間被覆層がない場合は、
直接基体層と表面被覆層が接着することにより基体層接
着面の凹凸が表面に影響し十分な平滑性が得られず、ま
た、基体層と表面被覆層の空隙状態の違いから一体感の
ない風合いとなり折れシボが悪くなる。この多孔質中間
被覆層に前記特徴を持たせるためにはその厚さ、スポン
ジ状態を適切な範囲に管理する必要がある。本発明にお
ける多孔質中間被覆層は、従来の湿式凝固した被覆層と
して多用されている厚さである数100μmに比べて極
めて薄く、また、気孔サイズも小さいものである。即
ち、その厚さは10〜40μm好ましくは15〜30μ
mである。厚さが10μm以下では表面の平滑性が十分
得られず、また、40μm以上では風合いが硬くなりや
すい。
The intermediate coating layer (skin layer) integrated with the base layer is an indispensable layer for obtaining surface smoothness, flexibility, moisture permeability, and a good sense of creasing. That is, it is located between the base layer and the dry porous surface coating layer, and has the functions of producing the above-mentioned characteristics and creating a preferable texture with a feeling of unity as a leather-like sheet. Without this intermediate coating layer,
By directly adhering the base layer and the surface coating layer, the unevenness of the base layer adhesion surface affects the surface and sufficient smoothness cannot be obtained, and there is no sense of unity due to the difference in the void state of the base layer and the surface coating layer. It becomes a texture and breaks and the texture becomes worse. In order for the porous intermediate coating layer to have the above characteristics, it is necessary to control the thickness and sponge state within an appropriate range. The porous intermediate coating layer in the present invention is extremely thin and has a small pore size as compared with the thickness of several 100 μm which is a thickness commonly used as a conventional wet-solidified coating layer. That is, its thickness is 10 to 40 μm, preferably 15 to 30 μm.
m. If the thickness is 10 μm or less, the smoothness of the surface is not sufficiently obtained, and if it is 40 μm or more, the texture tends to be hard.

【0011】また、中間被覆層の気孔の大きさとしては
断面に観察される気孔の90%以上の気孔の最大孔径が
1〜30μm好ましくは1〜10μmである。弾性重合
体を湿式凝固した場合、一般に気孔は厚み方向に縦長
で、最大孔径は1μm以上となりやすい。最大孔径が3
0μm以上となるような条件で凝固すると、中間被覆層
としての10〜40μmの厚さの膜ができにくくなる。
この孔はスキン層の内部のみではなく一部表面にも連通
し、透湿性、表面被覆層との接着性向上に寄与してい
る。なお、本発明でいう湿式膜多孔質中間被覆層の最大
孔径とは、該被覆層の縦断面を走査型電子顕微鏡等で少
なくとも1000倍、好ましくは3000倍に拡大して
観察したとき断面に観察される縦長の気孔の最大幅(最
大径に相当する幅)をいう。
Regarding the size of the pores of the intermediate coating layer, the maximum pore diameter of 90% or more of the pores observed in the cross section is 1 to 30 μm, preferably 1 to 10 μm. When the elastic polymer is wet-coagulated, the pores are generally elongated in the thickness direction, and the maximum pore diameter tends to be 1 μm or more. Maximum pore size is 3
When solidified under the condition that the thickness is 0 μm or more, it becomes difficult to form a film having a thickness of 10 to 40 μm as an intermediate coating layer.
The pores communicate not only with the inside of the skin layer but also with a part of the surface, which contributes to improvement of moisture permeability and adhesion to the surface coating layer. The maximum pore size of the wet membrane porous intermediate coating layer referred to in the present invention is the cross section of a longitudinal section of the coating layer observed at a magnification of at least 1000 times, preferably 3000 times with a scanning electron microscope or the like. The maximum width of the vertically elongated pores (width corresponding to the maximum diameter).

【0012】中間被覆層を形成する方法は、繊維集合体
に重合体組成液を含浸した後、湿式凝固に先だって表面
に中間被覆層となる弾性重合体組成液の塗膜を形成し湿
式凝固して基体層と同時に形成する方法、あるいは繊維
集合体に重合体組成液を含浸、凝固した後重合体組成液
をバーコートやナイフコートなどで塗布し湿式凝固して
中間被覆層を形成する方法があるが、中間被覆層と基体
層の一体性、コスト面から前者が好ましい。前者の場
合、重合体組成液の塗膜の形成方法は、繊維集合体に含
浸した弾性重合体液の液切りを行う際、液切りナイフと
繊維集合体との距離関係を調節して繊維集合体表面に含
浸用組成液の塗膜層を形成する方法、繊維集合体に弾性
重合体組成液を含浸、液切りした後中間被覆層用の弾性
重合体の組成液をバーコートやナイフコートなどで塗布
する方法などがあるが、塗膜厚さのコントロールのしや
すさ、工程の簡便さから含浸液の液切りと同時に中間被
覆層を形成することが好ましい。また、この中間被覆層
の弾性重合体は前記の如くポリウレタンが好ましく、基
体層のポリウレタンとの相溶性が良好な範囲でその種類
を選択できる。即ち、全体の風合い、剥離強力等を考慮
し、塗布液として使用するポリウレタンは、基体層用ポ
リウレタンと同種のポリウレタンであっても異なった種
類のポリウレタンであってもよく、また、ポリウレタン
溶液の濃度も同じであっても異なったものであってもよ
い。通常は、塗布に用いるポリウレタン溶液の濃度は含
浸用に使用するポリウレタン濃度と同じかそれよりも高
めのものを使用する。この中間被覆層のスポンジ状態は
塗布するウレタン組成液の濃度、添加剤の種類や量な
ど、凝固液の組成、温度などの凝固条件等を適宜選択す
ることにより調整可能であり、一般に、ポリウレタンの
濃度や粘度を大きくしたり、凝固浴の温度や溶剤濃度を
高くすると気孔の最大径は小さくなる傾向にある。使用
するポリウレタンの種類などに応じて最大孔径が1〜3
0μmとなる条件を選定する。
The intermediate coating layer is formed by impregnating the fiber assembly with the polymer composition liquid, forming a coating film of the elastic polymer composition liquid on the surface to form the intermediate coating layer prior to wet coagulation, and wet coagulating. Or a method of forming an intermediate coating layer by impregnating a fiber assembly with a polymer composition liquid and coagulating and then applying the polymer composition liquid by bar coating or knife coating and then wet coagulating. However, the former is preferable in terms of the integrity of the intermediate coating layer and the base layer and the cost. In the former case, the method for forming a coating film of the polymer composition liquid is such that when the elastic polymer liquid impregnated in the fiber assembly is drained, the distance relationship between the liquid cutting knife and the fiber assembly is adjusted. A method of forming a coating layer of the impregnating composition liquid on the surface, impregnating the fiber aggregate with the elastic polymer composition liquid, draining the composition liquid of the elastic polymer for the intermediate coating layer by bar coating, knife coating, etc. Although there are coating methods and the like, it is preferable to form the intermediate coating layer at the same time as draining of the impregnating liquid from the viewpoint of easy control of the coating film thickness and simplicity of the process. Further, as described above, the elastic polymer of the intermediate coating layer is preferably polyurethane, and the kind thereof can be selected within a range where the compatibility with the polyurethane of the base layer is good. That is, considering the overall texture, peel strength, etc., the polyurethane used as the coating solution may be the same polyurethane as the base layer polyurethane or a different type of polyurethane, and the concentration of the polyurethane solution may be different. May be the same or different. Usually, the concentration of the polyurethane solution used for coating is the same as or higher than the concentration of the polyurethane used for impregnation. The sponge state of the intermediate coating layer can be adjusted by appropriately selecting the concentration of the urethane composition liquid to be applied, the type and amount of additives, the composition of the coagulating liquid, the coagulation conditions such as temperature, and the like. When the concentration or viscosity is increased or the temperature of the coagulation bath or the solvent concentration is increased, the maximum pore diameter tends to decrease. Maximum pore size is 1-3 depending on the type of polyurethane used
Select the condition that gives 0 μm.

【0013】多孔質表面被覆層は本発明の最も重要な部
分である。即ち、柔軟性、ドレ−プ性、透湿性、外観の
高級感はこの表面被覆層の構成によって決まるところが
大である。湿式法による多孔質層は表面層としては強度
などの物性が十分ではないため、本発明においては表面
被覆層は乾式法により形成する。通常、多孔質乾式膜を
得る方法としては、発泡剤を利用する方法、反応により
発泡させる方法、機械発泡した塗布液を利用する方法、
および水抽出性微粒子を利用する方法があるが、前3者
は乾式膜の中で独立した気泡となりやすく孔が連続して
いないため透湿性を上げる効果がない。本発明では抽出
性粒子を利用する方法を検討して従来に無い条件を採用
し、厚さ20〜100μm、好ましくは30〜80μ
m、最大孔径20μmより大きい気孔が実質的に存在し
ないという新規な構造とした事により、前記の特徴を合
せ持つ皮革様シ−ト状物を得るに至った。最大孔径は、
好ましくは、倍率3000倍に拡大撮影した電子顕微鏡
写真上で気孔であると確認できる最大孔径0.2μm
(写真上での直径0.6mm)以上の気孔の80数量%
以上が10μm以下、30数量%以上が2μm以下、さ
らに好ましくは90数量%以上が10μm以下、50数
量%以上が2μm以下である。また、最大孔径の平均は
好ましくは1〜5μm、さらに好ましくは1〜3μmの
範囲である。なお、本発明における乾式膜多孔質表面被
覆層の最大孔径とは、該被覆層の縦断面を走査型電子顕
微鏡等で少なくとも3000倍に拡大して観察したとき
断面に観察される気孔の最大径をいう。具体的には、3
000倍に拡大撮影した電子顕微鏡写真上で少なくとも
600cm2(約6700μm2に相当)の領域におい
て、気孔として確認され得る直径0.6mm(直径0.
2μmに相当)以上の気孔について、6mm、30mm
及び60mmの円(それぞれ、2μm、10μm及び2
0μmに相当)を描いた透明シートを重ね、それぞれの
円内に気孔の全体が収まるか収まらないかにより最大径
の範囲を求める。それぞれの最大径の範囲に対応するの
気孔の数を数え、気孔の全体数に対するそれぞれの数量
比を求める。なお、本発明の乾式膜多孔質表面層の縦断
面に観察される気孔の多くは、連続するトンネル状の気
孔の横断面又は斜め断面であり、その長径と短径の比が
2以下の円形や楕円形が変形した形状である。断面に観
察される気孔の形状として、連続するトンネルの縦断面
に近い状態で長径と短径の比が2以上と長細い気孔形状
が観察される場合があるが、このような場合にはその最
大径は短径方向の最大幅を最大径とする。
The porous surface coating layer is the most important part of the present invention. That is, flexibility, drapeability, moisture permeability, and high-grade appearance are largely determined by the constitution of the surface coating layer. Since the porous layer formed by the wet method does not have sufficient physical properties such as strength as the surface layer, the surface coating layer is formed by the dry method in the present invention. Usually, as a method of obtaining a porous dry film, a method of using a foaming agent, a method of foaming by reaction, a method of using a mechanically foamed coating liquid,
There is also a method of using water-extractable fine particles, but the former three are not effective in improving the moisture permeability because they are likely to become independent bubbles in the dry membrane and the pores are not continuous. In the present invention, a method utilizing extractable particles has been examined and conditions not existing in the past have been adopted, and a thickness of 20 to 100 μm, preferably 30 to 80 μm.
m, and a new structure in which pores larger than the maximum pore diameter of 20 μm do not substantially exist has led to the obtainment of a leather-like sheet having the above characteristics. The maximum pore size is
Preferably, the maximum pore diameter that can be confirmed as pores on an electron micrograph taken at a magnification of 3000 times is 0.2 μm.
80% of pores (diameter 0.6mm in the photo) or more
The above is 10 μm or less, 30% by number or more is 2 μm or less, more preferably 90% by number or more is 10 μm or less, and 50% by number or more is 2 μm or less. The average maximum pore size is preferably 1 to 5 μm, more preferably 1 to 3 μm. The maximum pore diameter of the dry membrane porous surface coating layer in the present invention means the maximum diameter of the pores observed in the cross section when the vertical cross section of the coating layer is observed at least 3000 times with a scanning electron microscope or the like. Say. Specifically, 3
In an area of at least 600 cm 2 (corresponding to about 6700 μm 2 ) on an electron micrograph taken at a magnification of × 000, a diameter of 0.6 mm (diameter of 0.
6 mm, 30 mm for pores of 2 μm or more)
And 60 mm circles (2 μm, 10 μm and 2 respectively)
A transparent sheet having a thickness of 0 μm) is overlaid, and the maximum diameter range is determined depending on whether all the pores fit within each circle. The number of pores corresponding to each maximum diameter range is counted, and the ratio of each number to the total number of pores is obtained. Most of the pores observed in the vertical cross section of the dry membrane porous surface layer of the present invention are the cross section or diagonal cross section of continuous tunnel-shaped pores, and the ratio of the major axis to the minor axis is 2 or less. The elliptical shape is a deformed shape. As the shape of the pores observed in the cross section, a long and narrow pore shape with a ratio of the major axis to the minor axis of 2 or more may be observed in a state close to the longitudinal section of a continuous tunnel. The maximum diameter is the maximum width in the minor axis direction.

【0014】乾式膜多孔質表面被覆層の空隙率は、20
〜70%の範囲であることが好ましく、さらに、30〜
50%であることが好ましい。乾式膜多孔質層を構成す
る弾性体の種類や物性によっても異なるが、乾式膜多孔
質表面被覆層の空隙率が大きくなると、柔軟ではあるが
機械的強度が劣るものとなりやすく、小さくなるとゴム
ライクで反発感の大きい風合いとなりやすい。
The porosity of the dry membrane porous surface coating layer is 20.
Is preferably in the range of 70% to 70%, and more preferably 30 to
It is preferably 50%. Although it depends on the type and physical properties of the elastic body that constitutes the dry membrane porous layer, if the porosity of the dry membrane porous surface coating layer becomes large, it tends to be flexible but poor in mechanical strength, and if it becomes small, it becomes rubber-like. It tends to have a strong feeling of repulsion.

【0015】抽出性粒子を利用する造面法で優れた柔軟
性、透湿性、表面強度、好ましいタッチ、表面感を作り
出す主要条件としては 1)使用する弾性重合体の種類と積層条件 2)使用する抽出性粒子の種類、混入条件 3)塗工処理条件 が決め手となる。
The main conditions for producing excellent flexibility, moisture permeability, surface strength, favorable touch and surface feeling in the surface-forming method using extractable particles are 1) the type of elastic polymer used and the lamination conditions 2) used Type of extractable particles to be used and mixing conditions 3) Coating processing conditions are decisive factors.

【0016】1)使用する弾性重合体としては、前記の
基体層に含浸する樹脂条件で記載したごとく各種適用可
能だが、風合い、耐久性の点からポリウレタンを主体と
するのが好ましい。ポリウレタンとしては、前記含浸用
又は中間被覆層用のポリウレタンと同じものが使用で
き、ポリウレタンの組成は該皮革様シ−ト状物の指向す
る用途分野に応じて、風合い、耐摩耗性、耐劣化性、耐
黄変性、染色性等の各種物性を満足するものの中から適
宜選ぶことができる。基体層用あるいは中間被覆層用ポ
リウレタンが主として湿式凝固タイプとしての適性を持
つ必要があるのに対し、表面被覆層用ポリウレタンは乾
式膜タイプであり、湿式凝固性は必要としないが、耐摩
耗性等の耐久性が主として要求される。
1) The elastic polymer to be used can be variously applied as described in the resin conditions for impregnating the above-mentioned base layer, but it is preferable to mainly use polyurethane from the viewpoint of texture and durability. As the polyurethane, the same polyurethane as that for the impregnation or the intermediate coating layer can be used, and the composition of the polyurethane has a texture, abrasion resistance and deterioration resistance depending on the field of application in which the leather-like sheet material is intended. It can be appropriately selected from those satisfying various physical properties such as properties, yellowing resistance, and dyeability. Polyurethane for the base layer or intermediate coating layer needs to be suitable as a wet coagulation type mainly, whereas polyurethane for the surface coating layer is a dry film type, and does not require wet coagulation but wear resistance. Durability such as is mainly required.

【0017】離型紙上にポリウレタン溶液を塗布して基
体層に接着する乾式造面法で使用されるポリウレタン
は、通常、表面および中間層用として用いられる1液性
のものと、接着剤用として用いられる2液性で処理後架
橋硬化するものの2種類があり、接着剤用ポリウレタン
は基体層との接着力と表面層の被膜強度を上げる作用が
ある。本発明で使用する表面被覆層用ポリウレタンは表
皮および中間層用の1液性のものであり、2液性のもの
は使用しない。これは架橋硬化により粒子の抽出性を妨
げまた基体層を含めたシ−ト状物全体の風合いが悪くな
ることを避けるためである。なお、本発明における離型
紙とは、従来から人工皮革などの製造に使用されている
紙やフイルム等の表面に離型性樹脂などにより離型性を
付与され、かつ表面に凹凸模様や平滑面を有する離型性
のシートの総称である。
Polyurethanes used in the dry surface-forming method in which a polyurethane solution is coated on a release paper and adhered to a substrate layer are usually a one-component polyurethane used for the surface and the intermediate layer and an adhesive for the adhesive. There are two types of two-component resins used, which are cross-linked and cured after treatment, and polyurethane for adhesives has an effect of increasing the adhesive force with the base layer and the film strength of the surface layer. The polyurethane for the surface coating layer used in the present invention is a one-part type for the skin and the intermediate layer, and a two-part type is not used. This is in order to prevent the extractability of the particles from being impaired by cross-linking and to prevent the texture of the whole sheet-like material including the substrate layer from being deteriorated. Incidentally, the release paper in the present invention, the release property is imparted to the surface of paper or film conventionally used in the production of artificial leather or the like by a release resin, and the surface has an uneven pattern or a smooth surface. Is a general term for releasable sheets having.

【0018】これらの表面被覆層用樹脂は溶剤で溶解
し、着色剤、抽出性粒子等を混入して1層又は多層に分
けて塗布するが、好ましい表面感、タッチ、スキン層と
の接着性を得るには、多層に分け夫々異なる組成液で塗
布するのが良い。すなわち、離型性シートに最初に塗布
する表皮層は、好ましいタッチ、表面強度を得るためモ
ジュラスの高いポリウレタン又は接着性に問題のない範
囲でニトロセルロ−ズ樹脂を混入したりアミノ酸重合体
を用いる。また、次に塗布する表皮層との間の中間層で
は良好な風合い、透湿性を得るべくモジュラスの低いポ
リウレタンを選定し、抽出性粒子は膜強度に問題のない
範囲で多量に混入する。さらに、中間被覆層に接する接
着層部分では中間被覆層との接着性を重視し抽出性粒子
の混入量を低下させ、中間被覆層へ浸透しやすい粘度に
設定する。また、各層の塗布量は中間層を多めにし、中
間被覆層に接する層や表皮層はやや少なめとする。着色
剤は、発色性を考慮にいれ各層に同種又は異種の顔料又
は染料を混入する。
These surface coating layer resins are dissolved in a solvent and mixed with a colorant, extractable particles and the like and applied in a single layer or in multiple layers. However, preferable surface feeling, touch and adhesion to skin layer are preferable. In order to obtain the above, it is preferable to divide into multiple layers and apply different composition liquids. That is, for the skin layer first applied to the release sheet, polyurethane having a high modulus is used in order to obtain preferable touch and surface strength, or a nitrocellulose resin is mixed or an amino acid polymer is used within a range where there is no problem in adhesiveness. For the intermediate layer between the skin layer to be applied next, polyurethane having a low modulus is selected so as to obtain a good texture and moisture permeability, and the extractable particles are mixed in a large amount within the range where there is no problem in the film strength. Further, in the adhesive layer portion in contact with the intermediate coating layer, the adhesiveness with the intermediate coating layer is emphasized, the amount of the extractable particles mixed is reduced, and the viscosity is set to easily penetrate into the intermediate coating layer. Further, the coating amount of each layer is such that the amount of the intermediate layer is large and the amount of the layer in contact with the intermediate coating layer and the skin layer is slightly small. As for the colorant, the same or different pigments or dyes are mixed in each layer in consideration of color developability.

【0019】2)使用する抽出性粒子としては、必要な
粒度にまで微粉砕が可能なもので、かつ、水や熱水に容
易に溶解する事が必要で、例えば、塩化ナトリウム、硫
酸ナトリウム、等の無機化合物、ゼラチン、砂糖等の天
然有機物、ポリビニ−ルアルコ−ル、アンモニア変性し
た無水マレイン酸とイソブチレンの共重合体(例えば、
(株)クラレ社製イソバン:商品名)等の有機化合物が
挙げられるが、粒子の溶解性、微粒子化性、取扱い性等
から見てアンモニア変性した無水マレイン酸とイソブチ
レンの共重合体が最適である。即ち、塩化ナトリウム、
硫酸ナトリウム、等の無機化合物または砂糖等の有機物
ポリビニルアルコ−ル等の有機化合物は十分に微粒子化
出来にくく、また溶解性も不十分であり、ゼラチンは溶
解性は良好であるが吸湿性が大きく微粒子化が困難であ
るとともに取扱い性が悪い。
2) The extractable particles to be used are those that can be finely pulverized to the required particle size and that they can be easily dissolved in water or hot water. For example, sodium chloride, sodium sulfate, Inorganic compounds such as gelatin, natural organic substances such as sugar, polyvinyl alcohol, copolymers of maleic anhydride and isobutylene modified with ammonia (for example,
Examples include organic compounds such as Kuraray Co., Ltd.'s Isoban: trade name), but an ammonia-modified maleic anhydride-isobutylene copolymer is most suitable in view of particle solubility, fine particle size, handleability, and the like. is there. That is, sodium chloride,
Inorganic compounds such as sodium sulfate, and organic compounds such as sugar, organic compounds such as polyvinyl alcohol, etc. are difficult to form into fine particles, and the solubility is insufficient. Gelatin has good solubility but high hygroscopicity. It is difficult to make fine particles and handling is poor.

【0020】さらに、本発明で使用する抽出性微粒子
は、その一部が弾性重合体の溶剤に溶解し、しかも溶液
状態で弾性重合体溶液とは均一に混合せず相分離するこ
とが重要である。すなわち、本発明の乾式膜多孔質表面
層の連続した気孔と気孔サイズの分布は、弾性重合体の
溶剤に溶解しない微粒子を単に弾性重合体の溶液に混合
し抽出しただけでは得られない。微粒子の一部が弾性重
合体の溶剤に溶解することにより、微粒子はより小さく
なり、粉砕時のとがった角が丸みを帯びてくる。さら
に、溶解した微粒子の溶液が弾性重合体溶液と層分離し
た状態で存在することにより、微細なトンネル状の気孔
の形成に大きく寄与しているものと考えられる。抽出性
微粒子の弾性重合体の溶剤への溶解部分の比率は弾性重
合体溶液の濃度や粘度、抽出性微粒子の粒径などによっ
ても異なり必ずしも限定されるものではないが、目安と
しては該溶剤90部に熱水抽出性微粒子10部を加え9
0℃で30分攪拌した後の溶解分が5〜40重量%程度
である。溶解部分が少ないと微細な気孔が十分に形成さ
れず、また、溶解部分が多すぎると、気孔が微細になり
すぎ、風合いが硬いものとなりやすい。抽出性微粒子
は、必ずしも1種類である必要はなく、2種以上を混合
して用いることが出来る。また、十分に微粒子化するこ
とが可能であれば、弾性重合体の溶液に溶解しない抽出
性微粒子を併用することが出来、また、溶剤に一部溶解
する抽出性微粒子の代わりに、弾性重合体の溶液には溶
解するが弾性重合体溶液とは均一に混合せず、かつ該抽
出性微粒子と親和性の高い抽出性樹脂とを併用して用い
ることも出来る。
Further, it is important that a part of the extractable fine particles used in the present invention is dissolved in the solvent of the elastic polymer, and in the solution state, it is not uniformly mixed with the elastic polymer solution and phase-separated. is there. That is, the continuous pores and pore size distribution of the dry membrane porous surface layer of the present invention cannot be obtained by simply mixing fine particles of the elastic polymer which are not dissolved in the solvent with the elastic polymer solution and extracting. By dissolving a part of the fine particles in the solvent of the elastic polymer, the fine particles become smaller and the sharp corners at the time of pulverization become rounded. Furthermore, it is considered that the solution of the dissolved fine particles exists in a state of being separated from the elastic polymer solution in a layer state, which greatly contributes to the formation of fine tunnel-shaped pores. The ratio of the extractable fine particles to the dissolved portion of the elastic polymer in the solvent varies depending on the concentration and viscosity of the elastic polymer solution and the particle size of the extractable fine particles, and is not necessarily limited, but as a guideline, the solvent 90 Add 10 parts of hot water extractable fine particles to 9 parts
The dissolved content after stirring for 30 minutes at 0 ° C. is about 5 to 40% by weight. If the dissolved portion is small, fine pores are not sufficiently formed, and if the dissolved portion is too large, the pores are too fine and the texture tends to be hard. The extractable fine particles do not necessarily have to be one type, and two or more types can be mixed and used. In addition, if it is possible to sufficiently make fine particles, it is possible to use extractable fine particles which are not dissolved in the solution of the elastic polymer together, and instead of the extractable fine particles which are partially dissolved in the solvent, the elastic polymer is used. It is also possible to use in combination with the extractable fine particles which are soluble in the above solution but are not uniformly mixed with the elastic polymer solution and which have a high affinity.

【0021】前記した無水マレイン酸とイソブチレンの
共重合体は、アンモニア変性の程度を変えることによ
り、水に対する溶解性とジメチルホルムアミド等の有機
溶剤に対する溶解性をコントロールすることが出来る。
The above-mentioned copolymer of maleic anhydride and isobutylene can control the solubility in water and the solubility in an organic solvent such as dimethylformamide by changing the degree of ammonia modification.

【0022】抽出性微粒子の適切な平均粒度としては、
抽出後の多孔質層の気孔の大きさに関連して2〜20μ
m、好ましくは5〜10μmである。2μm以下では粒
子が凝集しやすくまた抽出性が悪くなり、20μm以上
では気孔が大きくなり過ぎ膜強度が低下しまた表面平滑
性が悪くなる。粒度分布としては1〜50μm程度で、
この中で2〜20μm部分が80%以上であることが好
ましい。弾性重合体の溶剤に部分溶解しない抽出性微粒
子を併用する場合には、弾性重合体溶液に混合後に微粒
子径が微細化しないため、より粒度の小さい微粒子を用
いることが必要であり、また、微粉砕したときのとがっ
た角が出来るだけ少ない微粒子を用いることが好まし
い。抽出性微粒子に鋭利な角が多いと、抽出後の多孔質
層がもろく機械的強度に劣ったものとなりやすい。
A suitable average particle size of the extractable fine particles is
2 to 20 μ in relation to the pore size of the porous layer after extraction
m, preferably 5 to 10 μm. If it is 2 μm or less, the particles tend to aggregate and the extractability is deteriorated. If it is 20 μm or more, the pores become too large and the film strength is lowered and the surface smoothness is deteriorated. The particle size distribution is about 1 to 50 μm,
It is preferable that the 2 to 20 μm portion is 80% or more. When the extractable fine particles that are not partially dissolved in the solvent of the elastic polymer are used together, it is necessary to use fine particles having a smaller particle size because the fine particle size does not become fine after mixing with the elastic polymer solution. It is preferable to use fine particles having as few sharp edges as possible when crushed. If the extractable fine particles have many sharp edges, the porous layer after extraction is fragile and the mechanical strength tends to be poor.

【0023】抽出性微粒子の表面被覆層樹脂への混入量
としては、表皮層は樹脂100重量部に対して0〜50
重量部、好ましくは0〜20重量部、中間層は樹脂10
0重量部に対して100〜300重量部、好ましくは1
50〜250重量部、スキン層と接する層は、樹脂10
0重量部に対して0〜50重量部、好ましくは0〜20
重量部である。表皮層において抽出性微粒子の混入量が
50重量部以上となると表面の離型性シートの模様が明
瞭に転写されずまた離型性シートに微粒子が付着しやす
い。中間層において抽出性微粒子の混入量が100重量
部以下では十分な多孔質構造が出来ず、また、300重
量部以上では気孔が合体し巨大空隙ができ膜強度が低下
する。中間被覆層と接する層において抽出性微粒子の混
入量が50重量部以上となると抽出後に中間被覆層との
接着面積が減少し、接着力が低下する。
The amount of the extractable fine particles mixed in the resin for the surface coating layer is 0 to 50 with respect to 100 parts by weight of the resin in the skin layer.
Parts by weight, preferably 0 to 20 parts by weight, the intermediate layer being resin 10
100 to 300 parts by weight, preferably 1 to 0 parts by weight
50 to 250 parts by weight, the layer in contact with the skin layer is resin 10
0 to 50 parts by weight, preferably 0 to 20 parts by weight
Parts by weight. When the amount of the extractable fine particles mixed in the surface layer is 50 parts by weight or more, the pattern of the release sheet on the surface is not clearly transferred, and the fine particles are easily attached to the release sheet. If the amount of the extractable fine particles mixed in the intermediate layer is 100 parts by weight or less, a sufficient porous structure cannot be obtained, and if it is 300 parts by weight or more, pores are coalesced to form huge voids and the film strength is lowered. When the amount of the extractable fine particles mixed in the layer in contact with the intermediate coating layer is 50 parts by weight or more, the area of adhesion to the intermediate coating layer after extraction is reduced and the adhesive strength is reduced.

【0024】抽出性微粒子の表面層樹脂への混入は分散
不良とならないように十分な撹拌と、凝集した微粒子の
濾過が必要である。本発明においては、抽出性微粒子が
部分溶解して微粒子の角が丸みを帯び、さらに微粒子化
するため、中間層の樹脂固形分に対して同量以上、3倍
にも達する量の微粒子を混合しても機械的強度に優れた
多孔質被覆層を得ることが出来る。
Mixing of the extractable fine particles into the surface layer resin requires sufficient stirring and filtration of the aggregated fine particles so as not to cause poor dispersion. In the present invention, since the extractable fine particles are partially dissolved and the corners of the fine particles are rounded and further made into fine particles, an amount equal to or more than three times the amount of fine particles of the resin solid content of the intermediate layer is mixed. Even then, a porous coating layer having excellent mechanical strength can be obtained.

【0025】3)塗工処理では、離型性シートの上に前
記した表皮層、中間層、接着層(スキンと接する層)の
順に各組成液を塗工し、最後に基体層と貼り合わせる
が、ここでは各塗工液の乾燥条件と貼り合わせ圧力条件
が重要なポイントである。即ち、抽出性微粒子が表面被
覆層の厚さ方向で互いに接し合った状態として、抽出後
連続した気孔を形成するためと、表皮面のシボ模様を鮮
明にするため、及び中間被覆層へ塗工液を有効に浸透さ
せ接着力を上げるために、処理銘柄に合わせて各塗工液
の乾燥条件と貼り合わせ圧力条件を調節する。各液塗工
後の乾燥条件が強すぎると表皮面のシボは鮮明となる
が、各層に混入した抽出性微粒子がそのまま固定され貼
り合わせ時に圧力をかけても移動せず抽出性微粒子が互
いに接した状態となりにくいため、抽出後連続した気孔
とならず十分な透湿性、風合いが得られないばかりか、
さらに、中間被覆層へ塗工液が十分浸透せず表面被覆層
と中間被覆層の間の接着力が低下する。逆に乾燥条件が
弱すぎると中間層の抽出性微粒子が表皮面に多量に移動
し表皮面のシボを不鮮明にする。また貼り合わせ圧力が
低すぎると各層の抽出性微粒子の移動が少なく、中間被
覆層への塗工液の浸透が不足し十分な透湿性、風合い、
接着力が出ない。逆に圧力が高すぎると接着力は高くな
るが、部分的に浸透過多になったり表皮面に抽出性微粒
子が集まり、表面の平滑性不良、シボの不鮮明状態を発
生させる。適切な条件で造面され、巻き取られた後は表
面層を十分に固定するため通常の乾式造面処理と同様2
日程度熟成するのが好ましい。
3) In the coating treatment, each composition liquid is coated on the release sheet in the order of the above-mentioned skin layer, intermediate layer, and adhesive layer (layer in contact with the skin), and finally laminated with the substrate layer. However, here, the drying condition of each coating liquid and the bonding pressure condition are important points. That is, in a state where the extractable fine particles are in contact with each other in the thickness direction of the surface coating layer, to form continuous pores after extraction, to make the textured pattern of the skin surface clear, and to coat the intermediate coating layer. In order to effectively permeate the liquid and increase the adhesive strength, the drying conditions and the bonding pressure conditions of each coating liquid are adjusted according to the treatment brand. If the drying conditions after coating each liquid are too strong, the surface texture of the skin becomes clear, but the extractable fine particles mixed in each layer are fixed as they are and do not move even when pressure is applied during bonding and the extractable fine particles contact each other. Since it is difficult to get into a state where it does not become continuous pores after extraction, sufficient moisture permeability and texture can not be obtained,
Furthermore, the coating liquid does not sufficiently penetrate into the intermediate coating layer, and the adhesive force between the surface coating layer and the intermediate coating layer decreases. On the other hand, if the drying conditions are too weak, a large amount of the extractable fine particles in the intermediate layer move to the surface of the skin, making the surface of the surface unclear. Further, when the bonding pressure is too low, the extractable fine particles in each layer are less likely to move, the penetration of the coating liquid into the intermediate coating layer is insufficient, and the sufficient moisture permeability, the texture,
The adhesive strength does not come out. On the other hand, if the pressure is too high, the adhesive strength will be high, but partial permeation will occur and extractable fine particles will collect on the surface of the skin, resulting in poor surface smoothness and unclear texture. After the surface is formed under appropriate conditions, and after being wound up, the surface layer is sufficiently fixed, so that it is the same as the normal dry surface preparation process.
It is preferable to age for about a day.

【0026】微粒子の抽出方法としては通常の染色機で
処理可能である。即ち、Dip−Nip法、ジッガ−
法、ウインス法、サ−キュラ−法等いずれでも可能だ
が、基体層のリラックス効果も合わせて得られるウイン
ス法、サ−キュラ−法がより適している。処理条件とし
ては、水温60℃〜100℃、処理時間40〜100分
程度でほとんどの微粒子が抽出され且つ基体層も十分リ
ラックスされる。この微粒子の抽出、リラックス処理に
より、表面被覆層は最大孔径が実質的に20μm以下で
その平均が1〜5μmの連続した気孔を有する乾式膜多
孔質表面被覆層に変成される。抽出性微粒子として弾性
重合体の溶液に部分溶解せず、粒子径の大きいゼラチン
微粒子を用いた場合には、該ゼラチン粒子を溶解除去し
ても表面被覆層には本発明のように極めて微細な気孔は
得られず、最大径は使用したゼラチン粒子の平均径より
大きくなることが多い。
As a method for extracting the fine particles, a usual dyeing machine can be used. That is, the Dip-Nip method and the jigger
Method, wince method, circular method, etc. are all possible, but the wince method and circular method are more suitable because the relaxing effect of the base layer is also obtained. As treatment conditions, a water temperature of 60 ° C. to 100 ° C. and a treatment time of about 40 to 100 minutes cause most of the fine particles to be extracted and the substrate layer to be sufficiently relaxed. By the extraction and relaxation treatment of the fine particles, the surface coating layer is transformed into a dry membrane porous surface coating layer having a maximum pore size of substantially 20 μm or less and continuous pores having an average of 1 to 5 μm. When gelatin fine particles having a large particle size which are not partially dissolved in the solution of the elastic polymer as the extractable fine particles are used, even if the gelatin particles are dissolved and removed, the surface coating layer is extremely fine as in the present invention. No pores are obtained and the maximum diameter is often larger than the average diameter of the gelatin particles used.

【0027】抽出処理後のシート状物は、必要に応じ
て、表面に高級感を付与するための追加の着色処理、カ
レンダ−処理等を組み合わせて実施する。さらに、本発
明のシート状物は、優れた柔軟性を付与するため柔軟剤
処理を行う。即ち、上記のようにして得られた本発明の
シート状物は、柔軟な皮革様シ−ト状物であるが、更に
柔軟剤処理を追加することにより、繊維相互及び繊維と
含浸樹脂との滑りを良くし、かつ多孔質のセルの中に柔
軟剤を存在させる事でしっとりとした独特の風合い、ド
レ−プ性を合せ持つ従来にない柔軟性に優れた高級皮革
様シ−ト状物が得られる。
If necessary, the sheet material after the extraction treatment is subjected to a combination of an additional coloring treatment for imparting a high-grade feeling to the surface, a calendar treatment and the like. Further, the sheet material of the present invention is treated with a softening agent in order to impart excellent flexibility. That is, the sheet-like article of the present invention obtained as described above is a flexible leather-like sheet-like article, but by further adding a softening agent treatment, it is possible to combine the fibers with each other and the fibers and the impregnated resin. A high-quality leather-like sheet with excellent slipperiness and unique softness due to the presence of a softening agent in the porous cells and drapeability. Is obtained.

【0028】柔軟剤処理はDip−Nip法で十分であ
る。処理剤としては、通常の柔軟剤、例えば、アミノシ
リコン系、エチレングリコ−ル系、各種油剤等適用可能
であるがその柔軟効果はもちろん浸透性、樹脂や繊維に
対する劣化性、各種堅牢度等を考慮にいれ選択する。柔
軟剤処理後は、柔軟剤の付与効果を高めるため機械揉み
処理を併用するのが好ましい。
As the softening agent treatment, the Dip-Nip method is sufficient. As the treating agent, a usual softening agent, for example, aminosilicone-based, ethylene glycol-based, various oil agents, etc. can be applied, but the softening effect is of course permeation, deterioration to resins and fibers, various fastnesses, etc. Take into consideration and select. After the treatment with the softening agent, it is preferable to use mechanical rubbing treatment together in order to enhance the imparting effect of the softening agent.

【0029】以上、本発明の骨格を記載したが、各種条
件を組み合わせることにより各種用途に適した高級な皮
革様シ−ト状物を得ることができる。本発明で得た皮革
様シ−ト状物は、優れた柔軟性、ドレ−プ性、高い透湿
性、高級な表面感を持つ皮革様シ−ト状物であり、衣
料、手袋、袋物、鞄、紳士婦人靴、スポ−ツシュ−ズ、
インテリア用途に適している。
Although the skeleton of the present invention has been described above, by combining various conditions, it is possible to obtain a high-quality leather-like sheet suitable for various uses. The leather-like sheet obtained in the present invention is a leather-like sheet having excellent flexibility, drape, high moisture permeability, and high-grade surface feeling, and is used for clothing, gloves, bags, Bag, men's ladies' shoes, sports shoes,
Suitable for interior use.

【0030】[0030]

【実施例】次に、本発明の実施態様を具体的な実施例で
説明するが、本発明はこれら実施例に限定されるもので
はない。なお実施例中の部および%は断りのない限り、
重量に関するものである。
EXAMPLES The embodiments of the present invention will now be described with reference to specific examples, but the present invention is not limited to these examples. The parts and% in the examples are unless otherwise specified.
It is about weight.

【0031】実施例−1 黒系顔料を練り込んだ6−ナイロンを分散成分、ポリエ
チレンを分散媒成分とする多成分繊維(成分比率は重量
比で1:1)からなる目付300g/m2の絡合不織布
に、黒系着色剤を含む高分子ジオール成分としてポリエ
チレンアジペ−トとポリエチレングリコ−ルを含むポリ
ウレタンの13%ジメチルホルムアミド(DMF)溶液
を含浸し、両面をドクターナイフで液切りして25%D
MF水溶液中で凝固した。このシートを乾燥後、熱トル
エンにより多成分繊維中のポリエチレンを溶解除去し
て、単繊度0.007デニールの極細繊維が約300本
集束した極細繊維束状繊維の不織布にポリウレタンが多
孔質状態で含有した基体層の両面に厚さ約30μm、最
大孔径が1〜10μmの多孔質のポリウレタンスキン層
が形成されたシ−ト得た。このシ−トを厚み方向でスラ
イス2分割し、1枚の表面に、乾式造面法で3層のポリ
ウレタン樹脂を塗布した。即ち、シボ模様を有する離型
性シート上に表皮層としてシリコン変性エ−テル系ポリ
ウレタン(大日本インキ株式会社製、UST−125C
P)の25%ジメチルホルムアミド溶液100部に、D
MF溶解分の重量が20%のアンモニア変性した無水マ
レイン酸とイソブチレンの共重合体の平均粒径8μmの
微粒子(以下イソバン微粒子という)を7部、黒顔料を
10部の割合で混入し十分撹拌した液を70g/m2塗布
し80℃で1分乾燥した後、エ−テル系ポリウレタン
(大日精化株式会社製、ME8105)の25%ジメチ
ルホルムアミド溶液100部に同じイソバン微粒子を5
0部、黒顔料を20部の割合で混入し十分撹拌した液を
120g/m2塗布し80℃で2分乾燥した後、さらに接
着層としてエ−テル系ポリウレタン(大日精化株式会社
製、ME8105)の25%ジメチルホルムアミド溶液
100部に同じイソバン微粒子を固形分比で10部の割
合で混入し十分撹拌した液を80g/m2塗布し、中間被
覆層の上にクリアランスロ−ルで貼り合わせた後100
℃で2分乾燥した。さらに2日間熟成させた後離型性シ
ートを剥離し、シ−トをサ−キュラ−液流染色機で90
℃で60分間リラックス処理し、イソバン微粒子を溶解
除去し乾燥した。次に、柔軟処理としてシリコン系柔軟
剤(日華株式会社製、ニッカシリコン/ラステックスの
混合物)の25%水溶液で2Dip−2Nip処理し、
乾燥した後、更に揉み処理を行って皮革様シ−ト状物に
仕上げた。
Example 1 A unit weight of 300 g / m 2 comprising multi-component fibers (dispersion ratio is 1: 1 by weight) of 6-nylon in which a black pigment is kneaded as a dispersion component and polyethylene as a dispersion medium component. The entangled nonwoven fabric was impregnated with a 13% dimethylformamide (DMF) solution of polyurethane containing polyethylene adipate and polyethylene glycol as a polymer diol component containing a black colorant, and drained on both sides with a doctor knife. 25% D
Coagulated in MF aqueous solution. After drying this sheet, polyethylene in the multi-component fiber was dissolved and removed with hot toluene, and the polyurethane was porous in the nonwoven fabric of ultrafine fiber bundle fibers in which about 300 ultrafine fibers with a single fineness of 0.007 denier were bundled. A sheet was obtained in which a porous polyurethane skin layer having a thickness of about 30 μm and a maximum pore size of 1 to 10 μm was formed on both sides of the contained substrate layer. This sheet was divided into two slices in the thickness direction, and three layers of polyurethane resin were applied to one surface by a dry surface-making method. That is, a silicone-modified ether type polyurethane (manufactured by Dainippon Ink and Chemical Co., Inc., UST-125C) as a skin layer on a release sheet having a texture pattern.
100 parts of 25% dimethylformamide solution of P), D
7 parts of fine particles (hereinafter referred to as isoban fine particles) having an average particle diameter of 8 μm of a copolymer of maleic anhydride and isobutylene modified with ammonia having a weight of 20% of MF dissolved therein and 10 parts of a black pigment are mixed sufficiently. The resulting solution was applied at 70 g / m 2 and dried at 80 ° C. for 1 minute, and then 5 parts of the same isoban fine particles were added to 100 parts of a 25% dimethylformamide solution of ether polyurethane (manufactured by Dainichiseika Co., Ltd., ME8105).
After mixing 120 parts of 0 part and a black pigment in a ratio of 20 parts and thoroughly stirring, 120 g / m 2 was applied and dried at 80 ° C. for 2 minutes, and then an ether type polyurethane (manufactured by Dainichiseika Co., Ltd., as an adhesive layer. ME8105) 25% dimethylformamide solution (100 parts) was mixed with the same isoban fine particles at a solid content ratio of 10 parts and well stirred, and a solution of 80 g / m 2 was applied, and the solution was applied onto the intermediate coating layer with a clearance roll. 100 after combining
It was dried at ℃ for 2 minutes. After aging for 2 more days, the release sheet was peeled off, and the sheet was put on a circular jet dyeing machine.
Relaxing treatment was performed at 60 ° C. for 60 minutes to dissolve and remove fine particles of isoban, followed by drying. Next, as a softening treatment, 2Dip-2Nip treatment was performed with a 25% aqueous solution of a silicone-based softening agent (Nikka Co., Ltd., Nikka Silicon / Lastex mixture),
After drying, it was further subjected to a rubbing treatment to finish into a leather-like sheet.

【0032】このシート状物の乾式多孔質被覆層の縦断
面を走査型電子顕微鏡により3000倍に拡大撮影し、
厚さと断面に現れた気孔の大きさを測定したところ、厚
さは70μmであり、最大孔径20μm以上の気孔は観
察されず、断面7000μm2あたりの最大孔径0.2
μm以上の気孔の総数は436個、その内10μm以下
の気孔は428個(98%)、2μm以下の気孔は31
5個(72%)、その平均は1.5μmであった。得ら
れたシ−ト状物は、風合いが特に良好で表面の高級感が
あり、豊かなドレ−プ性と高い透湿性を備えており衣料
用原反として非常に好ましいものであった。
A vertical cross section of the dry porous coating layer of the sheet-like material was magnified 3000 times with a scanning electron microscope,
When the thickness and the size of the pores appearing in the cross section were measured, the thickness was 70 μm, no pores with a maximum pore diameter of 20 μm or more were observed, and the maximum pore diameter per cross section 7,000 μm 2 was 0.2 μm.
The total number of pores of μm or more is 436, of which 428 are pores of 10 μm or less (98%) and 31 are pores of 2 μm or less.
Five (72%), the average of which was 1.5 μm. The obtained sheet-like material had a particularly good texture, a high-quality surface, a rich drape property and a high moisture permeability, and was very preferable as an original fabric cloth.

【0033】比較例−1 実施例−1において、柔軟剤処理を行わず揉み処理のみ
で仕上げ、皮革様シ−ト状物を得た。得られたシ−ト状
物は、表面の高級感はあるが実施例−1で得られたシ−
ト状物に比較し表面のソフトなタッチとドレ−プ性がや
や不足する原反であった。
Comparative Example-1 In Example-1, a leather-like sheet was obtained by finishing with only rubbing without the softening agent. The obtained sheet-like material has a high-quality surface, but the sheet obtained in Example-1.
It was a raw material that had a soft touch on the surface and a slightly insufficient drapability as compared with the tough material.

【0034】比較例−2〜4 実施例−1において、中間被覆層の厚みを0μm(付与
しないもの)、5μm及び70μmに変更する以外は実
施例−1と同じ工程により皮革様シ−ト状物に仕上げ
た。得られたシ−ト状物は、中間被覆層が0μm又は5
μmのものでは、風合い、ドレ−プ性、タッチ等は良好
で高い透湿性を有していたが、乾式多孔質表面被覆層の
厚さはそれぞれ50μm、65μmと基体層への樹脂の
沈み込みが大きく、実施例−1で得られたシ−ト状物に
比較し表面の平滑性に欠けまた巾方向の折れしわの残る
原反であった。また、中間被覆層が70μmのものでは
表面の平滑性は良好であったが、中間被覆層の気孔の最
大孔径は1〜60μmと大きく、風合いが硬く、ドレー
プ性に欠け、高級感に欠けるものであった。
Comparative Examples-2 to 4 In the same manner as in Example-1, except that the thickness of the intermediate coating layer is changed to 0 μm (not applied), 5 μm and 70 μm in Comparative Example-2, a leather-like sheet is formed. I finished it. The obtained sheet-like material has an intermediate coating layer of 0 μm or 5
In the case of μm, the texture, drapability, touch, etc. were good and had high moisture permeability, but the thickness of the dry type porous surface coating layer was 50 μm and 65 μm, respectively, and the resin sunk into the substrate layer. Was larger than that of the sheet-like material obtained in Example 1 and lacked in surface smoothness and had wrinkles in the width direction. The surface smoothness was good when the intermediate coating layer had a thickness of 70 μm, but the maximum pore diameter of the intermediate coating layer was large at 1 to 60 μm, the texture was hard, the drape property was lacking, and the feeling of luxury was lacking. Met.

【0035】比較例−5 実施例−1において、イソバン微粒子の代わりに平均粒
子15μmのゼラチン微粒子を用いる以外は同条件でシ
ート状物に仕上げた。得られたシート状物の表面被覆層
の断面を顕微鏡観察すると、厚みが85μmで、気孔の
最大径は2〜30μmの範囲であり、10μm以下の気
孔は40%、2μm以下の気孔は8%であった。この皮
革様シート状物は、ソフトではあるが、ドレープ性やし
っとりした触感に欠け、高級感に欠けるものであった。
Comparative Example-5 A sheet-like material was finished under the same conditions as in Example-1, except that gelatin fine particles having an average particle size of 15 μm were used in place of the isoban fine particles. When the cross section of the surface coating layer of the obtained sheet-like material is observed under a microscope, the thickness is 85 μm, the maximum diameter of the pores is in the range of 2 to 30 μm, the pores of 10 μm or less are 40%, and the pores of 2 μm or less are 8%. Met. Although this leather-like sheet was soft, it lacked drape and moist feel, and lacked a high-class feel.

【0036】比較例−6 中間被覆層の厚さが5μmである他は実施例−1と同じ
構成の基体層を用いその表面に湿式法により表面被覆層
を付与した。即ち、コ−ト液として100%モジュラス
が30kg/cm2のエ−テル系ポリウレタンを用い、その
13%DMF溶液を350g/m2中間被覆層の表面に塗
工し、25℃の水で凝固させた。このシ−トの表面に黒
顔料を混入したエ−テル系ポリウレタン8%(イソプロ
ピルアルコール−トルエン溶剤)溶液を150メッシュ
で2回塗布した後、ヤンピ−シボでエンボスし、最後に
実施例−1と同じ柔軟処理を行って皮革様シ−ト状物に
仕上げた。得られたシ−ト状物は、表面湿式多孔質層
は、厚さが70μm、気孔の最大孔径が10〜60μm
であり、実施例−1で得られたシ−ト状物に比較し風合
いが硬く表面の平滑性も不足し高級感に欠け、透湿性も
低い原反であった。
Comparative Example 6 A substrate layer having the same constitution as in Example 1 except that the thickness of the intermediate coating layer was 5 μm was used, and a surface coating layer was applied to the surface by a wet method. That is, an ether type polyurethane having a 100% modulus of 30 kg / cm 2 was used as a coating solution, and a 13% DMF solution thereof was coated on the surface of an intermediate coating layer of 350 g / m 2 and coagulated with water at 25 ° C. Let An ether type polyurethane 8% (isopropyl alcohol-toluene solvent) solution mixed with a black pigment was applied twice to the surface of this sheet with 150 mesh, followed by embossing with a yanpi-texture, and finally Example-1. The same softening treatment as described above was applied to finish into a leather-like sheet. The obtained sheet-like material had a surface wet porous layer having a thickness of 70 μm and a maximum pore diameter of 10 to 60 μm.
In comparison with the sheet-like material obtained in Example 1, the texture was hard, the surface was lacking in smoothness, lacked in high-grade feeling, and was low in moisture permeability.

【0037】比較例−7 比較例−2の中間被覆層を付与しない基体層を用い、そ
の表面に透湿性のある多孔質の乾式皮膜層を付与した。
即ち、離型性シート上に透湿性ポリウレタンの溶液(大
日精化株式会社製、ハイムレンX−3038)100
部、黒顔料20部、メチルエチルケトン18部、トルエ
ン18部、水50部、架橋剤としてレザミンX(商品
名:大日精化株式会社製)2部、レザミンUM−317
(商品名:大日精化株式会社製)2部の配合液を300
g/m2塗布し80℃で2分乾燥させた後基体層表面に積
層し、さらに130℃で2分加熱し造面した。この後実
施例−1と同じ柔軟処理を行って皮革様シ−ト状物に仕
上げた。このシート状物の表面被覆層を顕微鏡観察した
ところ、厚みは72μmで、気孔の最大径は5〜20μ
mと比較的大きく、しかも数が少なく、連通した気孔も
少なかった。得られたシ−ト状物は、実施例−1で得ら
れたシ−ト状物に比較し表面がやや硬い風合いとなり、
自然な折れしわ感の不足する原反であった。
COMPARATIVE EXAMPLE-7 A base layer having no intermediate coating layer of Comparative Example-2 was used, and a porous dry coating layer having moisture permeability was provided on the surface thereof.
That is, a solution of a moisture-permeable polyurethane (Heimren X-3038, manufactured by Dainichiseika Co., Ltd.) 100 on the releasable sheet.
Parts, 20 parts of black pigment, 18 parts of methyl ethyl ketone, 18 parts of toluene, 50 parts of water, 2 parts of Resamine X (trade name: manufactured by Dainichiseika Co., Ltd.) as a crosslinking agent, Resamine UM-317.
(Product name: manufactured by Dainichiseika Co., Ltd.)
After coating at g / m 2 and drying at 80 ° C. for 2 minutes, it was laminated on the surface of the substrate layer and further heated at 130 ° C. for 2 minutes to produce a surface. Thereafter, the same softening treatment as in Example-1 was carried out to finish a leather-like sheet. Microscopic observation of the surface coating layer of this sheet material revealed that the thickness was 72 μm and the maximum pore diameter was 5 to 20 μm.
m was relatively large, and the number was small, and there were few communicating pores. The obtained sheet-like material had a slightly harder surface than the sheet-like article obtained in Example-1,
It was a raw material that lacked a natural sense of creasing.

【0038】比較例−8 実施例−1と同じ基体層を用い乾式造面において、接着
層に通常の2液型ポリウレタンを使用する以外は実施例
−1と同じ処理を行い皮革様シ−ト状物に仕上げた。即
ち、接着層としてエ−テル系ポリウレタン(大日精化株
式会社製、UD8310)100部、ジメチルホルムア
ミド30部、メチルエチルケトン20部、架橋剤(大日
精化株式会社製、NE架橋剤)12部、促進剤(大日精
化株式会社製、UD−103)8部、平均粒径8μmの
イソバン30部を混合し十分撹拌した液を80g/m2
布した。得られたシ−ト状物は、実施例−1で得られた
シ−ト状物に比較し風合いやタッチが悪く透湿性もかな
り低い原反であった。
Comparative Example-8 A leather-like sheet was prepared by using the same substrate layer as in Example-1 and performing the same treatment as in Example-1 except that a normal two-component polyurethane was used for the adhesive layer on the dry surface. It was finished in the shape. That is, 100 parts of an ether polyurethane (UD8310 manufactured by Dainichiseika Co., Ltd.) as an adhesive layer, 30 parts of dimethylformamide, 20 parts of methyl ethyl ketone, 12 parts of a cross-linking agent (NE cross-linking agent manufactured by Dainichiseika Co., Ltd.), acceleration 80 g / m 2 of a solution (8 parts by weight of UD-103 manufactured by Dainichiseika Co., Ltd.) and 30 parts of isoban having an average particle size of 8 μm were mixed and sufficiently stirred. The sheet-like product obtained was a raw fabric having a poor texture and touch and a considerably low moisture permeability as compared with the sheet-like product obtained in Example-1.

【0039】実施例−2 ポリエチレンテレフタレ−トを分散成分(平均単繊度
0.003デニール)、ポリエチレンを分散媒成分(重
量比1:1)とする多成分繊維からなる目付520g/
m2の絡合不織布に、青系顔料を含むポリエチレンアジペ
−ト/ポリエチレングリコ−ル共重合系ポリウレタンの
18%ジメチルホルムアミド(DMF)溶液を含浸し、
その表面に同種の溶液を40g/m2ナイフコ−トして2
5%DMF水溶液中で凝固後ポリエチレンを溶解除去し
て表面に多孔質層(中間層)を有する基体層を得た。こ
の基体層は、極細繊維束状繊維の不織布にポリウレタン
が多孔質状態で含有し、その表面に平均厚さ20μm、
最大孔径が1〜15μmの多孔質のポリウレタンスキン
層が形成されたシ−トとなった。この基体層シ−トの表
面に、乾式造面法で3層のポリウレタン樹脂を塗布し
た。即ち、離型性シート上に表皮層としてエ−テル系ポ
リウレタン(大日精化株式会社製、ME8115)25
%溶液100部に白顔料20部の割合で混入し十分撹拌
した液を70g/m2塗布し、80℃で1分乾燥した後中
間層としてエ−テル系ポリウレタン(大日精化株式会社
製、ME8105)25%溶液100部に実施例1のソ
バン微粒子を50部、白顔料を20部の割合で混入し十
分撹拌した液を150g/m2塗布し、80℃で2分乾燥
した後接着層としてエ−テル系ポリウレタン(大日精化
株式会社製、ME8105)25%溶液100部に同じ
イソバン微粒子を6部の割合で混入し十分撹拌した液を
80g/m2塗布し、基体層とクリアランスロ−ルで貼り
合わせた後100℃で2分乾燥した。熟成2日の後、離
型性シートを剥離したシ−トをサ−キュラ−液流染色機
で100℃60分リラックスし乾燥した。次に、ヌメリ
剤(セイコ−化成株式会社製、U−981)をグラビア
コ−トで100メッシュ1段塗布した後実施例−1と同
じ柔軟処理を行って皮革様シ−ト状物に仕上げた。
Example-2 Polyethylene terephthalate as a dispersion component (average fineness of 0.003 denier) and polyethylene as a dispersion medium component (weight ratio 1: 1), a unit weight of 520 g /
An 18% dimethylformamide (DMF) solution of polyethylene adipate / polyethylene glycol copolymer polyurethane containing a blue pigment was impregnated into the entangled nonwoven fabric of m 2 ,
40g / m 2 knife coat the same kind of solution on the surface and
After coagulation in a 5% DMF aqueous solution, polyethylene was dissolved and removed to obtain a base layer having a porous layer (intermediate layer) on the surface. This base layer contains polyurethane in a porous state in a nonwoven fabric of ultrafine fiber bundle fibers, and has an average thickness of 20 μm on the surface thereof.
The sheet was formed with a porous polyurethane skin layer having a maximum pore size of 1 to 15 μm. Three layers of polyurethane resin were applied to the surface of the base layer sheet by a dry surface-forming method. That is, as a skin layer on the releasable sheet, an ether type polyurethane (ME8115 manufactured by Dainichiseika Co., Ltd.) 25
% Solution of 100 parts by weight and mixed with 20 parts of white pigment and sufficiently stirred to apply 70 g / m 2 of liquid, and after drying at 80 ° C. for 1 minute, an ether type polyurethane (manufactured by Dainichiseika Co., Ltd., as an intermediate layer. ME8105) 50 parts of Soban fine particles of Example 1 and 20 parts of white pigment were mixed in 100 parts of 25% solution, and a well-stirred solution was applied at 150 g / m 2 and dried at 80 ° C. for 2 minutes, and then an adhesive layer As a solution of ether polyurethane (ME8105, manufactured by Dainichiseika Co., Ltd.), 100 parts of 25% solution was mixed with the same isoban fine particles at a ratio of 6 parts, and a well stirred solution was applied at 80 g / m 2 to form a base layer and a clearance layer. And then dried at 100 ° C. for 2 minutes. After 2 days of aging, the sheet from which the release sheet had been peeled off was relaxed and dried at 100 ° C. for 60 minutes with a circular jet dyeing machine. Next, a slime agent (manufactured by Seiko Kasei Co., Ltd., U-981) was applied in one step of 100 mesh with a gravure coat, and then the same softening treatment as in Example-1 was performed to finish into a leather-like sheet. It was

【0040】このシート状物の乾式多孔質被覆層の縦断
面を走査型電子顕微鏡により3000倍に拡大撮影し、
厚みと断面に現れた気孔の大きさを測定したところ、厚
みは75μmであり、最大孔径20μm以上の気孔は観
察されず、断面積7000μm2あたりの最大孔径0.
2μm以上の気孔の総数は505個、その内10μm以
下の気孔は478個(94%)、2μm以下の気孔は3
99個(79%)で、その平均は1.7μmであった。
得られたシ−ト状物は、ソフトで腰のある風合いを有し
表面は平滑でヌメリ感のあるタッチが得られ、十分な表
面表度と高い透湿性を兼ね備えておりスポ−ツシュ−ズ
用高級原反として適切な物であった。各実施例、比較例
で得られた皮革様シ−ト状物の評価結果を表1に示す。
A vertical cross section of the dry porous coating layer of the sheet-like material was photographed with a scanning electron microscope at a magnification of 3000 times,
When the thickness and the size of the pores appearing in the cross section were measured, the thickness was 75 μm, no pores with a maximum pore diameter of 20 μm or more were observed, and the maximum pore diameter per cross-sectional area of 7,000 μm 2 was 0.
The total number of pores of 2 μm or more is 505, of which 478 are 10 μm or less (94%) and 3 are 2 μm or less.
The number was 99 (79%), and the average was 1.7 μm.
The obtained sheet-like material has a soft and chewy texture, a smooth surface, and a touch with a slimy feel, and has a sufficient surface appearance and high moisture permeability, and the spot shoes It was suitable as a high-grade raw material. Table 1 shows the evaluation results of the leather-like sheet obtained in each Example and Comparative Example.

【0041】[0041]

【表1】 [Table 1]

【0042】物性測定方法 透湿度 JIS L1099−A1 テ−バ−摩耗 JIS L1096−6・17・3 屈曲性(FLEXO) JIS K6545 表面被覆層の空隙率は、断面で観察される気孔の面積比
率で表した。
Physical Properties Measuring Method Moisture Permeability JIS L1099-A1 Taber Wear JIS L1096-6 ・ 17 ・ 3 Flexibility (FLEXO) JIS K6545 The porosity of the surface coating layer is the area ratio of pores observed in the cross section. expressed.

【0043】表中の記号 (官能検査) ◎:極めて優れる ○:優れる △:やや劣る ×:劣る (テーバー摩耗) A:表面損傷なし B:表面損傷小 C:表面損傷中 D:表面損傷大 E:基体層露出 (屈曲性) A:表面割れなし B:表面割れ程度小 C:表面割れ程度中 D:表面割れ程度大 E:基体層穴あきSymbols in the table (Sensory test) ◎: Excellent ○: Excellent Δ: Slightly inferior ×: Inferior (Taber abrasion) A: No surface damage B: Small surface damage C: Medium surface damage D: Large surface damage E : Base layer exposed (flexibility) A: No surface crack B: Small degree of surface crack C: Medium degree of surface crack D: Large degree of surface crack E: Perforated base layer

【0044】[0044]

【発明の効果】本発明の皮革様シート状物は、高い透湿
性、優れた柔軟性、ドレ−プ性、天然皮革に類似したス
ム−スで高級感のある外観を合せ持つ皮革様シート状物
であり、高級銀付き衣料、各種手袋、ソフトなスポーツ
シューズ用途等に好適に使用される。
Industrial Applicability The leather-like sheet material of the present invention is a leather-like sheet material having high moisture permeability, excellent flexibility, drapeability, and a smooth and high-class appearance similar to natural leather. It is suitable for clothing such as high-grade silver clothing, various gloves, and soft sports shoes.

フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 D06N 3/14 8016−4F // C08L 75:04 Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location D06N 3/14 8016-4F // C08L 75:04

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 繊維集合体に弾性重合体を含有した基体
層の表面に弾性重合体の被覆層を有するシ−ト状物にお
いて、該被覆層が基体層と一体化され、かつ縦断面で観
察した最大孔径1〜30μmの連続した気孔を有する厚
さ10〜40μmの湿式多孔質中間被覆層と、微粒子を
抽出除去して得られ断面で観察した最大孔径が実質的に
20μm以下の連続した気孔を有する厚さ20〜100
μmの乾式多孔質表面被覆層の2層から構成され、かつ
両層とも柔軟剤を含有することを特徴とする柔軟性に優
れた皮革様シ−ト状物。
1. A sheet-shaped article having a coating layer of an elastic polymer on the surface of a substrate layer containing an elastic polymer in a fiber assembly, the coating layer being integrated with the substrate layer and having a longitudinal section. The wet porous intermediate coating layer having a continuous pore size of 1 to 30 μm and a thickness of 10 to 40 μm, and the maximum pore size of the cross section obtained by extracting and removing fine particles were substantially 20 μm or less. 20-100 thickness with pores
A leather-like sheet having excellent flexibility, which is composed of two layers of a dry porous surface coating layer having a thickness of .mu.m, and both layers contain a softening agent.
【請求項2】 (a) シート状の繊維集合体を形成する工
程、(b) 該繊維集合体に弾性重合体の組成液を含浸し凝
固して繊維集合体に弾性重合体を含有した基体層を形成
する工程、(c) 該繊維集合体の表面に弾性重合体の組成
液を塗布し湿式凝固して基体層と一体化された厚さ10
〜40μmで断面で観察した最大孔径1〜30μmの気
孔を有する湿式多孔質中間被覆層を形成する工程、(d)
離型紙上に弾性重合体の溶液に熱水抽出性微粒子を混入
した弾性重合体組成液を塗布し該湿式多孔質中間被覆層
上に貼合せ乾燥した後離型紙を剥離し乾式膜を形成する
工程、(e) 該乾式膜から該熱水抽出性微粒子を熱水抽出
することにより断面で観察した最大孔径0.5〜20μ
mの連続した気孔を有する厚さ20〜100μmの乾式
多孔質表面被覆層に変性する工程、(f) 少なくとも湿式
多孔質中間被覆層と乾式多孔質表面被覆層に柔軟剤を付
与する工程、を組み合わせることを特徴とする柔軟性に
優れた皮革様シ−ト状物の製造方法。
2. A substrate comprising (a) a step of forming a sheet-shaped fiber aggregate, and (b) an impregnation of a composition liquid of an elastic polymer into the fiber aggregate and coagulation to solidify the fiber aggregate to contain the elastic polymer. A step of forming a layer, (c) a thickness of 10 which is integrated with a base layer by applying a composition liquid of an elastic polymer on the surface of the fiber assembly and wet-coagulating it.
A step of forming a wet porous intermediate coating layer having pores with a maximum pore size of 1 to 30 μm observed in a cross section at ˜40 μm, (d)
An elastic polymer composition liquid prepared by mixing hot water extractable fine particles into a solution of an elastic polymer is applied onto a release paper, and the wet porous intermediate coating layer is laminated and dried, and then the release paper is peeled off to form a dry film. Step (e) The maximum pore diameter observed in the cross section by hot water extraction of the hot water extractable fine particles from the dry membrane is 0.5 to 20 μm.
m, a step of modifying to a dry porous surface coating layer having a thickness of 20 to 100 μm having continuous pores, and (f) a step of applying a softening agent to at least the wet porous intermediate coating layer and the dry porous surface coating layer. A method for producing a leather-like sheet having excellent flexibility, which is characterized by being combined.
JP5052694A 1993-03-25 1994-03-22 Leather-like sheet excellent in flexibility and method for producing the same Expired - Fee Related JP3142103B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5052694A JP3142103B2 (en) 1993-03-25 1994-03-22 Leather-like sheet excellent in flexibility and method for producing the same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP6677693 1993-03-25
JP5-66776 1993-03-25
JP5052694A JP3142103B2 (en) 1993-03-25 1994-03-22 Leather-like sheet excellent in flexibility and method for producing the same

Publications (2)

Publication Number Publication Date
JPH06330474A true JPH06330474A (en) 1994-11-29
JP3142103B2 JP3142103B2 (en) 2001-03-07

Family

ID=26391006

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP3142103B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999024658A1 (en) * 1997-11-10 1999-05-20 Teijin Limited Leather-like sheet and process for the production thereof
KR100448698B1 (en) * 2001-07-06 2004-09-16 씨엔이티 주식회사 Manufacturing method for artificial leather
JP2009228187A (en) * 2008-03-25 2009-10-08 Hiramatsu Sangyo Kk Leather-like and sheet-like article and method for producing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999024658A1 (en) * 1997-11-10 1999-05-20 Teijin Limited Leather-like sheet and process for the production thereof
CN1085276C (en) * 1997-11-10 2002-05-22 帝人株式会社 Leather-like sheet and process for production thereof
KR100448698B1 (en) * 2001-07-06 2004-09-16 씨엔이티 주식회사 Manufacturing method for artificial leather
JP2009228187A (en) * 2008-03-25 2009-10-08 Hiramatsu Sangyo Kk Leather-like and sheet-like article and method for producing the same

Also Published As

Publication number Publication date
JP3142103B2 (en) 2001-03-07

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