JP3059849B2 - Artificial leather with silver - Google Patents
Artificial leather with silverInfo
- Publication number
- JP3059849B2 JP3059849B2 JP4359255A JP35925592A JP3059849B2 JP 3059849 B2 JP3059849 B2 JP 3059849B2 JP 4359255 A JP4359255 A JP 4359255A JP 35925592 A JP35925592 A JP 35925592A JP 3059849 B2 JP3059849 B2 JP 3059849B2
- Authority
- JP
- Japan
- Prior art keywords
- skin layer
- silver
- artificial leather
- polyurethane elastomer
- wet
- 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.)
- Expired - Lifetime
Links
- 229910052709 silver Inorganic materials 0.000 title claims description 28
- 239000004332 silver Substances 0.000 title claims description 28
- 239000002649 leather substitute Substances 0.000 title claims description 23
- 239000010410 layer Substances 0.000 claims description 40
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000010985 leather Substances 0.000 description 9
- 230000015271 coagulation Effects 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- -1 acryl Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、天然皮革類似の表面タ
ッチと外観と柔らかな風合いを有する銀付人工皮革に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to artificial leather with silver having a surface touch similar to that of natural leather, an appearance and a soft texture.
【０００２】[0002]
【従来の技術】従来より、人工皮革などの皮革代替品の
表面タッチ及び外観を天然皮革に近づけるため、種々の
表面仕上げが行われている。例えば基材にポリウレタン
樹脂の水混和性有機溶剤溶液をコーティングし、水中に
浸漬してポリウレタン樹脂を湿式凝固せしめたいわゆる
湿式銀面には、熱エンボスによる型押し加工、グラビア
による着色、艶調整がなされる。一方、離型紙上にポリ
ウレタン等の薄膜を形成し、基材と接着後離型紙を剥離
するいわゆる乾式銀面法では、離型紙のシボによって、
天然皮革調の外観を施そうとしている。あるいは、上記
湿式銀面上に乾式銀面を形成するいわゆる湿乾併用によ
り、良好な風合い、外観、タッチを得ようとする試みも
なされている。2. Description of the Related Art Conventionally, various surface finishes have been performed to make the surface touch and appearance of a leather substitute such as artificial leather close to that of natural leather. For example, a so-called wet silver surface obtained by coating a base material with a water-miscible organic solvent solution of a polyurethane resin and immersing it in water to wet-solidify the polyurethane resin is embossed by hot embossing, coloring by gravure, and gloss control. Done. On the other hand, in the so-called dry silver surface method in which a thin film of polyurethane or the like is formed on release paper and the release paper is peeled off after bonding with the base material,
Trying to give it a natural leather look. Alternatively, attempts have been made to obtain a good texture, appearance, and touch by using a so-called wet-dry combination of forming a dry silver surface on the wet silver surface.
【０００３】しかし、これらの方法で得られる皮革代替
品は、いずれもその表面が乾式成膜によるものであるた
め、ノンポーラスで画一的なものであり、天然皮革の持
つ繊細なタッチおよび自然な艶消し感を実現することは
困難であった。このような画一的な外観および合成的な
タッチを改善するために、例えばコラーゲンなどの天然
高分子微粉末を表面樹脂原料に添加せしめ、表皮層に該
微粉末を突出させたり、あるいは、水溶性高分子微粉末
を表面樹脂原料に添加し、成膜後、該微粉末を溶出せし
め、表面に微小な孔を形成させる方法がある。[0003] However, the leather substitutes obtained by these methods are all non-porous and uniform because their surfaces are formed by dry film formation, and have the delicate touch and natural touch of natural leather. It was difficult to achieve a natural matte feeling. In order to improve such uniform appearance and synthetic touch, for example, a natural polymer fine powder such as collagen is added to the surface resin raw material, and the fine powder is projected to the skin layer, or water-soluble. There is a method in which a conductive polymer fine powder is added to a surface resin raw material, and after film formation, the fine powder is eluted to form fine pores on the surface.
【０００４】しかしながら、前者は、微粉末の粒径が大
きいため（平均粒径５μｍ以上）、表面タッチがザラつ
き、また、タッチ、外観など表面だけに影響を与えるよ
うに添加するのは難しく、効果を得ようとして添加部数
を上げれば、樹脂と微粉末とが膠着して風合いが硬化
し、皮膜強度が著しく低下してしまう。一方後者は、こ
れも表面タッチ、外観など表面だけを改善するように添
加するのは難しく、添加部数を上げれば、溶出させるタ
イプであるため、皮膜強度が著しく低下する。また、微
粉末の粒径が大きいため（平均粒径５μｍ以上）、外観
の艶消し感に劣る。更に両者とも経済的な面で不利であ
る。However, in the former, since the fine powder has a large particle size (average particle size of 5 μm or more), it is difficult to add such that the surface touch is rough and the touch, appearance, and the like are affected only on the surface. If the number of added parts is increased in order to obtain the effect, the resin and the fine powder adhere to each other, the texture is hardened, and the film strength is significantly reduced. On the other hand, the latter is also difficult to be added so as to improve only the surface such as surface touch and appearance, and if the number of added portions is increased, it is a type of elution, so that the film strength is significantly reduced. Further, since the fine powder has a large particle size (average particle size of 5 μm or more), the matte appearance is poor. In addition, both are economically disadvantageous.
【０００５】[0005]
【発明が解決しようとする課題】従って本発明の目的と
するところは、上述したような従来技術の問題点に鑑
み、表面タッチおよび外観が天然皮革に非常に類似し、
風合いの良好な銀付人工皮革を提供するにある。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention in view of the above-mentioned problems of the prior art that the surface touch and appearance are very similar to natural leather,
An object of the present invention is to provide a silvery artificial leather having a good texture.
【０００６】[0006]
【課題を解決するための手段】上述の目的を達成するた
め、本発明は次の通りの構成からなる。すなわち、繊維
集合体を骨格とする基材層と、その片面に積層されたポ
リウレタンエラストマーを主体とする多孔質銀面層と、
更にその表面に形成されたポリウレタンエラストマーを
主体とする表皮層から成り、該表皮層は平均厚さ５〜５
０μｍの微細多孔質構造を有し、表面には０．１〜８μ
ｍの孔及び又は凹部の内径が０．１〜８μｍ、凸部の高
さが３μｍ未満の凹凸が１×１０4 個／ｍｍ2 以上存在
することを特徴とする銀付人工皮革である。In order to achieve the above object, the present invention has the following arrangement. That is, a base material layer having a fiber aggregate as a skeleton, and a porous silver surface layer mainly composed of a polyurethane elastomer laminated on one surface thereof,
Further, it comprises a skin layer mainly composed of a polyurethane elastomer formed on the surface, and the skin layer has an average thickness of 5 to 5 mm.
It has a microporous structure of 0 μm, and has a surface of 0.1 to 8 μm.
m of holes and or the inner diameter of the recess 0.1～8Myuemu, a grain-artificial leather height of the convex portion, characterized in that the unevenness of less than 3μm is present 1 × 10 4 pieces / mm 2 or more.
【０００７】また、かかる本発明の銀付人工皮革におい
て、好ましくは、表皮層の平均厚さが１０〜３０μｍで
あり、あるいはまた、好ましくは、表面の孔もしくは凹
凸が５×１０4 個／ｍｍ2 以上存在し、更にまた、好ま
しくは、表皮層の表面がしぼ状に凝固形成されているも
のである。In the artificial leather with silver according to the present invention, preferably, the average thickness of the skin layer is 10 to 30 μm, or preferably, the number of pores or irregularities on the surface is 5 × 10 4 / mm. There are two or more, and more preferably, the surface of the skin layer is solidified and formed in a grain shape.
【０００８】以下、更に詳しく本発明について説明す
る。本発明の人工皮革は、湿式多孔質銀面上に水蒸気凝
固よりなる非常に薄い表皮層を持ち、該表皮層表面に形
成された微小な孔もしくは凹凸により天然皮革に極似し
たタッチと外観を有する点に特徴がある。Hereinafter, the present invention will be described in more detail. The artificial leather of the present invention has a very thin skin layer formed by steam coagulation on a wet porous silver surface, and has a touch and appearance very similar to natural leather due to minute holes or irregularities formed on the surface of the skin layer. There is a characteristic in having.
【０００９】本発明でいう基材とは繊維集合体を構造の
骨格とするシート状物、即ち合成繊維、天然繊維からな
る織物、編物及びこれらの起毛加工物、または不織布等
の繊維集合体そのもの、及びこれらの繊維集合体にバイ
ンダー加工されたもの等を言う。通常、繊維としては工
業的に容易に入手できる綿，羊毛，絹，レーヨン，アク
リル，ナイロン，ポリエステル等が用いられる。また、
より天然皮革に近い風合いを得るために、ナイロン，ポ
リエステル等からなる公知の極細繊維を用いることもで
きる。一般に基材の密度としては、０．１５〜０．５０
ｇ／ｃｍ3 が好ましく、特に好ましい範囲は０．２５〜
０．４５ｇ／ｃｍ3 である。In the present invention, the term "substrate" refers to a sheet-like material having a fiber aggregate structure as a skeleton, that is, a woven or knitted fabric composed of synthetic fibers or natural fibers, a brushed product thereof, or a fiber aggregate itself such as a nonwoven fabric. And those obtained by subjecting these fiber aggregates to binder processing. Usually, cotton, wool, silk, rayon, acryl, nylon, polyester, etc., which are industrially easily available, are used as the fibers. Also,
In order to obtain a texture closer to that of natural leather, known ultrafine fibers made of nylon, polyester, or the like can be used. Generally, the density of the substrate is 0.15 to 0.50
g / cm 3 is preferable, and a particularly preferable range is 0.25 to
0.45 g / cm 3 .
【００１０】バインダーとしてはポリウレタン、ポリス
チレンブタジエンラバーまたはそれらの共重合物が好ま
しく用いられるが、これらに限定されるものではない。
バインダー加工の方法としては湿式凝固法、乾式凝固法
等が採用され、風合いや弾性などを考慮して人工皮革
（皮革類似品）として好ましい範囲に繊維とバインダー
の重量比を調節する。繊維単独の場合は、風合いはソフ
トであるが腰がなく又二次製品化が困難な場合があるた
め、通常はバインダー加工された基材が好ましく使用さ
れる。As the binder, polyurethane, polystyrene butadiene rubber or a copolymer thereof is preferably used, but is not limited thereto.
As a method of processing the binder, a wet coagulation method, a dry coagulation method, or the like is employed, and the weight ratio of the fiber and the binder is adjusted to a preferable range as an artificial leather (leather-like product) in consideration of the feeling and elasticity. In the case of the fiber alone, the texture is soft but it is not firm, and it may be difficult to produce a secondary product. Therefore, a binder-processed base material is usually preferably used.
【００１１】次に、基材上に積層される多孔質銀面層お
よびその表面の微細多孔質構造を有する表皮層を形成す
るポリウレタンエラストマーについて述べる。ポリウレ
タンエラストマーとは、ポリオールと有機ジイソシアネ
ートと鎖伸長剤からなる主としてウレタン結合により高
分子化されたポリマーをいう。該ポリマーを主体として
他のポリマーを少量例えば５〜３０重量％混合してもよ
い。他のポリマーとしては、その目的によって適宜選択
されるが、ポリウレタンエラストマーの溶媒に溶解する
ものが好ましい。更には無機、有機系の充填剤や着色
剤、その他公知の添加物を混合してもよい。Next, a polyurethane elastomer which forms a porous silver surface layer laminated on a substrate and a skin layer having a fine porous structure on the surface thereof will be described. The polyurethane elastomer refers to a polymer composed of a polyol, an organic diisocyanate, and a chain extender, which is polymerized mainly by urethane bonds. A small amount, for example, 5 to 30% by weight of another polymer may be mixed mainly with the polymer. The other polymer is appropriately selected depending on the purpose, but is preferably a polymer soluble in a solvent of the polyurethane elastomer. Further, inorganic or organic fillers, coloring agents, and other known additives may be mixed.
【００１２】本発明で用いられるポリウレタンエラスト
マーは、特に限定するものではなく、公知のものが使用
できる。ポリウレタンエラストマーのポリオール成分
は、両末端に水酸基を有する分子量５００〜３０００の
化合物であり、ポリエステルジオール，ポリエーテルジ
オール，ポリカーボネートジオールあるいはこれらの共
重合物である。本発明品の表皮層には耐久性に優れるポ
リエーテルジオール，ポリカーボネートジオールあるい
はこれらの共重合物を用いることが好ましい。The polyurethane elastomer used in the present invention is not particularly limited, and known polyurethane elastomers can be used. The polyol component of the polyurethane elastomer is a compound having a hydroxyl group at both terminals and a molecular weight of 500 to 3000, and is a polyester diol, a polyether diol, a polycarbonate diol, or a copolymer thereof. For the skin layer of the product of the present invention, it is preferable to use polyether diol, polycarbonate diol, or a copolymer thereof, which has excellent durability.
【００１３】有機ジイソシアネートとしては４，４−ジ
フェニルメタンジイソシアネート（ＭＤＩ）、２，４−
トリレンジイソシアネートなどがよく用いられるが、耐
光性の良好なものが必要な場合はイソホロンジイソシア
ネートあるいは水添ＭＤＩを用いる。本発明に於て、特
に表皮層には、これらイソホロンジイソシアネートある
いは水添ＭＤＩを用いることが好ましい。As the organic diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), 2,4-
Tolylene diisocyanate or the like is often used, but if a material having good light resistance is required, isophorone diisocyanate or hydrogenated MDI is used. In the present invention, it is preferable to use these isophorone diisocyanates or hydrogenated MDI especially for the skin layer.
【００１４】さらに鎖伸長剤としては２以上の活性水素
を有する炭素数が２ないし６の低分子ジオールあるいは
ジアミンが用いられる。Further, as the chain extender, a low molecular weight diol or diamine having 2 or more active hydrogens and having 2 to 6 carbon atoms is used.
【００１５】中間層の多孔質銀面層は、ポリウレタンエ
ラストマーの水混和性有機溶剤溶液を湿式凝固して形成
されるものであれば、特に限定するものではなく、公知
の方法により作成することが出来る。The porous silver surface layer of the intermediate layer is not particularly limited as long as it is formed by wet coagulation of a water-miscible organic solvent solution of a polyurethane elastomer, and may be prepared by a known method. I can do it.
【００１６】表皮層である微細多孔質層は、ポリウレタ
ンエラストマーの有機溶剤溶液を水蒸気凝固することに
より形成される。水蒸気凝固方法としては、例えば湿式
銀面付基材上に前記ポリウレタンエラストマー溶液をコ
ーティングし、このコーティングした湿式銀面付基材を
一定湿度と温度の雰囲気中に暴露し、その雰囲気中の水
分により凝固させる方法、あるいは、支持体上に前記ポ
リウレタンエラストマー溶液をコーティングし、その上
に水湿潤化された湿式銀面付基材を積層し、次いで湿式
銀面付基材を介して加熱し、該湿式銀面付基材内に生じ
る飽和水蒸気により前記ポリウレタンエラストマーを実
質的に凝固せしめた後、支持体より離型し乾燥する方
法、あるいは、支持体上に前記ポリウレタンエラストマ
ー溶液をコーティングし、その上に湿式銀面付基材を積
層し、そのまま一定湿度と温度の雰囲気中に暴露し、そ
の雰囲気中の水分により凝固せしめた後、支持体より離
型し乾燥する方法などがある。The microporous layer serving as the skin layer is formed by coagulating a polyurethane elastomer solution in an organic solvent with steam. As a steam coagulation method, for example, the polyurethane elastomer solution is coated on a wet silver surface-coated substrate, and the coated wet silver surface-coated substrate is exposed to an atmosphere of a constant humidity and temperature, and the moisture in the atmosphere is used. A method of coagulation, or coating the polyurethane elastomer solution on a support, laminating a wet-grained substrate with water wet thereon, and then heating through the wet-grained substrate, After substantially coagulating the polyurethane elastomer with saturated water vapor generated in the wet-grained substrate, a method of releasing from the support and drying, or coating the polyurethane elastomer solution on a support, The base material with a wet silver surface was laminated on it, exposed to an atmosphere of constant humidity and temperature as it was, and coagulated by the moisture in the atmosphere. , It demolded from the support and a method of drying.
【００１７】本発明では、該表皮層の凝固後の平均厚み
が５〜５０μｍ、好ましくは１０〜３０μｍとなるよう
に前記ポリウレタンエラストマー溶液中のポリウレタン
固型分濃度を勘案して、塗布量を適宜調節する。該表皮
層の平均厚みが５０μｍよりも厚いと、風合いが硬くな
り、５μｍよりも薄いと均一で平滑な面を得にくい。ま
た、該表皮層の平均厚味が１０〜３０μｍであれば、風
合いおよび面平滑性という点で更に良好なものが得ら
れ、好ましい。ここで、塗布量が非常に少ないため、該
表皮層の面平滑性を出すためには、上記した支持体上に
ポリウレタンエラストマー溶液をコーティングする方法
が望ましい。更にまた、表皮層表面をしぼ状に凝固形成
させるために、上記した支持体が所望のしぼに対して逆
転彫刻加工または型押しされた支持体であることが望ま
しい。In the present invention, the coating amount is appropriately adjusted in consideration of the concentration of the polyurethane solid component in the polyurethane elastomer solution so that the average thickness of the skin layer after solidification is 5 to 50 μm, preferably 10 to 30 μm. Adjust. If the average thickness of the skin layer is larger than 50 μm, the texture becomes hard, and if it is smaller than 5 μm, it is difficult to obtain a uniform and smooth surface. In addition, when the average thickness of the skin layer is 10 to 30 μm, a more favorable texture and surface smoothness are obtained, which is preferable. Here, since the coating amount is very small, the above-mentioned method of coating the support with a polyurethane elastomer solution is desirable in order to improve the surface smoothness of the skin layer. Furthermore, in order to form the surface of the skin layer into a grain-like solidified form, it is preferable that the above-mentioned support is a support obtained by reversely engraving or embossing a desired grain.
【００１８】本発明における上記表皮層には、その表面
に０．１〜８μｍの孔もしくは凹部の内径が０．１〜８
μｍで凸部の高さが３μｍ未満の凹凸を１×１０4 個／
ｍｍ 2 以上存在し、好ましくは、表面の孔もしくは凹凸
が５×１０4 個／ｍｍ2 以上存在するもの、また凹凸の
凹部の内径が０．１〜３μｍであるものである。表面の
孔および凹部の内径が８μｍを超えると外観の艶消し感
およびタッチが粗くなってしまい、一方０．１μｍ未満
では表面タッチにいわゆるサラサラした感じがなくなっ
てしまう。また、凹凸の凸部の高さが３μｍ以上では、
外観の艶消し感およびタッチに劣る。また、該表面の孔
および凹凸の数が１×１０4 個／ｍｍ2未満では、外観
の艶消し感およびタッチに十分な影響を及ぼさない。The surface layer according to the present invention has a surface
The inner diameter of the hole or concave portion of 0.1 to 8 μm is 0.1 to 8
1 × 10 unevenness with a height of less than 3 μmFourPieces/
mm TwoOr more, preferably surface pores or irregularities
Is 5 × 10FourPieces / mmTwoWhat exists above,
The inner diameter of the recess is 0.1 to 3 μm. Surface
When the inner diameter of the holes and recesses exceeds 8 μm, the matte appearance
And the touch becomes coarse, but less than 0.1 μm
Then the so-called smooth feeling on the surface touch disappeared
Would. In addition, when the height of the convex portion of the unevenness is 3 μm or more,
Poor matte appearance and touch. Also, holes on the surface
And the number of irregularities is 1 × 10FourPieces / mmTwoLess than the appearance
Does not have a sufficient effect on the matte feeling and touch of the touch panel.
【００１９】これらの孔および凹凸を有する表皮層は、
乾式銀面に天然高分子微粉末を添加して得られる凹凸を
持つ表皮層のように、ポリウレタンエラストマー中に該
微粉末が突出していることに起因するザラザラしたタッ
チを有するものではない。また、乾式銀面における水溶
性高分子微粉末の溶出によって形成される孔および凹凸
を持つ表皮層のように、不連続で、皮膜強度にかけるも
のではなく、孔および凹凸を有するにもかかわらず十分
な皮膜強度を持つものである。The skin layer having these holes and irregularities is
Like a skin layer having irregularities obtained by adding a natural polymer fine powder to a dry silver surface, it does not have a rough touch due to the protrusion of the fine powder in the polyurethane elastomer. Also, like the skin layer having pores and irregularities formed by elution of the water-soluble polymer fine powder on the dry silver surface, it is not discontinuous and does not apply to the film strength, but has pores and irregularities It has sufficient film strength.
【００２０】本発明の銀付人工皮革は、断面の１００倍
の顕微鏡写真によれば、繊維骨格の基材上に湿式銀面層
を有し、更にその上に約２０μｍの平均厚みの表皮層が
形成されており、また表皮層の断面の７５０倍の顕微鏡
写真および表面の７５０倍の顕微鏡写真によれば、上述
せる表皮層の表面には微小な孔および凹凸が非常に数多
く存在することが観察される。The artificial leather with silver according to the present invention has a wet silver surface layer on a fiber skeleton base material and a skin layer having an average thickness of about 20 μm on the fiber skeleton base material according to a micrograph of 100 times the cross section. According to a 750-fold micrograph of the cross section of the skin layer and a 750-fold micrograph of the surface, it is found that the surface of the skin layer described above has a very large number of minute holes and irregularities. To be observed.
【００２１】[0021]
【発明の効果】以上本発明の構成については詳述した
が、本発明の最大の特徴の一つは、人工皮革の仕上げ表
面において、従来の乾式法によるノンポーラスで画一的
な仕上げ表面ではなく、水蒸気凝固による微小な孔およ
び凹凸を多数持つことによって、天然皮革に非常に類似
した外観の艶消し感とタッチを有する仕上げ表面が得ら
れる点にある。また、従来のいわゆる湿乾併用のような
最表皮層が乾式銀面のものと比べ、風合いがソフトであ
り、なおかつ、コラーゲンなどの天然微粉末を添加する
方法に比べて、外観、タッチ、皮膜強度、コスト面の全
ての点で優れる点にある。本発明の銀付人工皮革は、靴
甲皮、靴裏材、鞄等の袋物類、衣料用、家具等のインテ
リア用等、天然皮革に代わるべき幅広い用途に有用であ
る。As described above, the configuration of the present invention has been described in detail. One of the greatest features of the present invention is that a non-porous and uniform finished surface by the conventional dry method is used for the finished surface of artificial leather. In addition, by having many fine pores and irregularities due to steam coagulation, a finished surface having a matte feeling and a touch very similar in appearance to natural leather can be obtained. In addition, the texture is softer than that of a conventional dry-grain surface such as the so-called wet-dry combination, and the appearance, touch, and coating are lower than with the method of adding natural fine powder such as collagen. It is excellent in all aspects of strength and cost. The artificial leather with silver of the present invention is useful for a wide range of uses that can replace natural leather, such as shoe uppers, shoe backings, bags such as bags, clothing, interiors such as furniture, and the like.
【００２２】[0022]
【実施例】次に、本発明を実施例により具体的に説明す
る。尚、実施例中の部または％はことわりのない限り重
量に関するものである。Next, the present invention will be described in detail with reference to examples. In the examples, parts and% relate to weight unless otherwise specified.
【００２３】実施例１ 繊度０．２デニールのナイロン極細繊維束の３次元絡合
不織布にポリカーボネート系ポリウレタンが多孔質構造
となって充填された、繊維と樹脂との比率が４５／５
５、厚みが０．８０ｍｍ、密度が０．３５０ｇ／ｃｍ3
の基材に、ポリカーボネート系ポリウレタンの２０％ジ
メチルフォルムアミド（ＤＭＦ）溶液をドクターコータ
ーによって、２５０ｇ／ｍ2 塗布し、水中にて湿式凝固
し、湿式銀面付未仕上げ反を得た。次いでこの未仕上反
を含水率８０％に水湿潤加工した。Example 1 A three-dimensional entangled nonwoven fabric of a nylon fine fiber bundle having a fineness of 0.2 denier was filled with a polycarbonate-based polyurethane in a porous structure, and the ratio of fiber to resin was 45/5.
5. Thickness 0.80mm, density 0.350g / cm 3
A 20% dimethylformamide (DMF) solution of a polycarbonate-based polyurethane was applied at 250 g / m 2 by a doctor coater to the base material, and wet-solidified in water to obtain a wet-finished unfinished surface with a silver surface. Next, the unfinished fabric was subjected to wet processing to a water content of 80%.
【００２４】表皮層用ポリウレタンエラストマー溶液と
して、ポリオール成分にポリカーボネートジオール、有
機ジイソシアネート成分に水添ＭＤＩを用いた無黄変型
ポリカーボネート系ポリウレタンの固形分濃度２３％の
ＤＭＦ／トルエン／イソプロピルアルコール＝２／１／
１混合溶液を調製した。なおこのものはポリウレタンエ
ラストマーに対して０．５重量％のカーボンブラックで
着色されている。As the polyurethane elastomer solution for the skin layer, DMF / toluene / isopropyl alcohol with a solid concentration of 23% of non-yellowing type polycarbonate polyurethane using polycarbonate diol as a polyol component and hydrogenated MDI as an organic diisocyanate component = 2/1. /
One mixed solution was prepared. This is colored with 0.5% by weight of carbon black based on the polyurethane elastomer.
【００２５】フラットで光沢付きの離型紙上に上記ポリ
ウレタンエラストマー溶液を５０ｇ／ｍ2 で塗布した
後、直ちに前記の水湿潤加工された未仕上げ反を均一に
重ね合わせ、その上方から熱ロールにて５分間加熱し、
離型紙から表面仕上げ加工された湿式銀面付き基材を剥
離し、更に１２０℃で乾燥して残留溶剤及び水分を蒸発
させた。After applying the above polyurethane elastomer solution at 50 g / m 2 onto a flat glossy release paper, immediately, the unfinished fabric subjected to the water wet processing is immediately superposed uniformly, and a hot roll is applied from above. Heat for 5 minutes,
The surface-finished base material with a wet silver surface was peeled from the release paper, and dried at 120 ° C. to evaporate the residual solvent and moisture.
【００２６】得られた人工皮革の表面仕上げ層は、平均
厚み２０μｍの微細多孔質構造を有し、表面に０．３〜
２．０μｍの孔と凹部の内径が０．３〜２．０μｍ、凸
部の高さが１μｍ以下の凹凸を合わせて１．３×１０5
個／ｍｍ2 有し、外観の艶消し感、表面タッチ、風合い
共に良好であった。The surface finishing layer of the artificial leather thus obtained has a fine porous structure with an average thickness of 20 μm, and has a surface of 0.3 to 0.3 μm.
A total of 1.3 × 10 5 holes and 2.0 μm and concave and convex portions having an inner diameter of 0.3 to 2.0 μm and a convex portion having a height of 1 μm or less are combined.
Pcs / mm 2 , and the matte appearance, surface touch, and texture were good.
【００２７】実施例２ 実施例１と同様にして湿式銀面付き基材を得た。但し水
湿潤加工は行わなかった。キッド調シボ付き離型紙上に
実施例１の表皮層用ポリウレタンエラストマー溶液を５
０ｇ／ｍ2 塗布し、直ちに前記湿式銀面付き基材を均一
に重ね合わせ、温度６０℃、湿度９０％の雰囲気中に２
０分間暴露し、離型紙から表面仕上げ加工された湿式銀
面付き基材を剥離し、更に１２０℃で乾燥して残留溶剤
及び水分を蒸発させた。Example 2 A substrate having a wet silver surface was obtained in the same manner as in Example 1. However, no water wet processing was performed. The polyurethane elastomer solution for the skin layer of Example 1
0 g / m 2 , and immediately superimpose the above-mentioned wet-grained substrate uniformly on the substrate.
Exposure was performed for 0 minutes, the surface-finished base material with a wet surface was peeled from the release paper, and further dried at 120 ° C. to evaporate residual solvent and moisture.
【００２８】得られた人工皮革の表面仕上げ層は、平均
厚み１７μｍの微細多孔質構造を有し、表面に０．３〜
２．０μｍの孔と凹部の内径が０．３〜２．０μｍ、凸
部の高さが１μｍ以下の凹凸を合わせて１．０×１０5
個／ｍｍ2 有し、外観、表面タッチ、風合い共にキッド
に類似した非常に良好なものであった。The surface finishing layer of the artificial leather thus obtained has a fine porous structure with an average thickness of 17 μm, and has a surface of 0.3 to 0.3 μm.
A total of 1.0 × 10 5 holes and 2.0 μm and concave and convex portions having an inner diameter of 0.3 to 2.0 μm and a convex portion having a height of 1 μm or less are combined.
Pcs / mm 2 , and was very good in appearance, surface touch and texture similar to kid.
【００２９】比較例１ 表皮層用ポリウレタンエラストマー溶液の塗布量を１５
０ｇ／ｍ2 とした以外、実施例１と同様にして銀付人工
皮革を製造した。得られた人工皮革の表面仕上げ層は、
平均厚み６０μｍの微細多孔質構造で表面の孔と凹凸は
十分有していたが、風合いが硬いため表面タッチとして
も不十分なものであった。Comparative Example 1 The coating amount of the polyurethane elastomer solution for the skin layer was 15
An artificial leather with silver was produced in the same manner as in Example 1 except that the amount was changed to 0 g / m 2 . The surface finishing layer of the obtained artificial leather,
Although it had a microporous structure with an average thickness of 60 μm and had sufficient pores and irregularities on the surface, the texture was hard and the surface touch was insufficient.
【００３０】比較例２ 実施例１の表皮層用ポリウレタンエラストマー溶液中
に、平均粒子径１０μｍのコラーゲン微粉末をポリウレ
タンエラストマーに対して５０部添加した塗布液を、キ
ッド調シボ付き離型紙上に６０ｇ／ｍ2 の割合で塗布し
乾式凝固後、さらにその上に架橋型のポリウレタン系接
着剤を厚み３０μｍとなるように塗布し、いわゆる乾式
銀面法により、実施例１に示す湿式銀面付き基材を貼合
わせた。得られた人工皮革の表皮層は、その表面に外径
１０μｍ程度の凸部を１．０×１０3 個／ｍｍ2 程度し
か有さず、外観の艶消し感、および表面タッチが不十分
で、風合いも硬く劣るものであった。Comparative Example 2 A coating solution obtained by adding 50 parts of a collagen fine powder having an average particle size of 10 μm to the polyurethane elastomer in the polyurethane elastomer solution for the skin layer of Example 1 on a release paper with a kid-like grain was added in an amount of 60 g. / M 2 , and after dry coagulation, a cross-linkable polyurethane adhesive is further applied thereon so as to have a thickness of 30 μm. Materials were pasted together. The skin layer of the obtained artificial leather has only about 1.0 × 10 3 protrusions / mm 2 with an outer diameter of about 10 μm on the surface thereof, and the appearance of matte appearance and surface touch are insufficient. The texture was hard and inferior.
【００３１】比較例３ 実施例１の表皮層用ポリウレタンエラストマー溶液中
に、平均粒子径１０μｍのキトサン微粉末をポリウレタ
ンエラストマーに対して７０部添加した塗布液を用い、
比較例２と同様にして湿式銀面付き基材を貼合わせた。
その後、７０℃の温水にて２０分間洗浄して、キトサン
微粉末を溶出させた。得られた人工皮革の表皮層は、キ
トサンの溶出孔をその断面及び表面に持つが、表面に８
μｍ程度の孔を１．５×１０3 個／ｍｍ2 程度しか有さ
ず、外観の艶消し感、および表面タッチが不十分で、ま
た皮膜強度にも劣るものであった。Comparative Example 3 Using a coating liquid obtained by adding 70 parts of a chitosan fine powder having an average particle diameter of 10 μm to the polyurethane elastomer in the polyurethane elastomer solution for the skin layer of Example 1,
In the same manner as in Comparative Example 2, a substrate with a wet silver surface was laminated.
Thereafter, the resultant was washed with 70 ° C. warm water for 20 minutes to elute the chitosan fine powder. The skin layer of the obtained artificial leather has chitosan elution holes on its cross section and on the surface.
It had only about 1.5 × 10 3 holes / mm 2 having pores of about μm, and had poor matte appearance, insufficient surface touch, and poor film strength.
Claims (4)
片面に積層されたポリウレタンエラストマーを主体とす
る多孔質銀面層と、更にその表面に形成されたポリウレ
タンエラストマーを主体とする表皮層から成り、該表皮
層は平均厚さ５〜５０μｍの微細多孔質構造を有し、表
面には０．１〜８μｍの孔及び／又は凹部の内径が０．
１〜８μｍで凸部の高さが３μｍ未満の凹凸が１×１０
4 個／ｍｍ2 以上存在することを特徴とする銀付人工皮
革。1. A base layer having a fiber aggregate as a skeleton, a porous silver surface layer mainly composed of a polyurethane elastomer laminated on one surface thereof, and a skin mainly composed of a polyurethane elastomer formed on the surface thereof. The skin layer has a microporous structure having an average thickness of 5 to 50 μm, and the surface has a pore and / or recess having an inner diameter of 0.1 to 8 μm of 0.1 to 8 μm.
1 × 10 unevenness with a height of less than 3 μm at 1 to 8 μm
Artificial leather with silver, characterized in that there are at least 4 / mm 2 .
る請求項１記載の銀付人工皮革。2. The artificial leather with silver according to claim 1, wherein the average thickness of the skin layer is 10 to 30 μm.
０4 個／ｍｍ2 以上存在する請求項１記載の銀付人工皮
革。3. The surface of the skin layer has pores or irregularities of 5 × 1.
0 4 / mm 2 or more existing claim 1, wherein the grain-artificial leather.
いる請求項１記載の銀付人工皮革。4. The artificial leather with silver according to claim 1, wherein the surface of the skin layer is solidified and formed in a grain shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4359255A JP3059849B2 (en) | 1992-12-25 | 1992-12-25 | Artificial leather with silver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4359255A JP3059849B2 (en) | 1992-12-25 | 1992-12-25 | Artificial leather with silver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06192966A JPH06192966A (en) | 1994-07-12 |
| JP3059849B2 true JP3059849B2 (en) | 2000-07-04 |
Family
ID=18463561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4359255A Expired - Lifetime JP3059849B2 (en) | 1992-12-25 | 1992-12-25 | Artificial leather with silver |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3059849B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3187357B2 (en) * | 1997-11-10 | 2001-07-11 | 帝人株式会社 | Leather-like sheet and method for producing the same |
| KR20010079123A (en) * | 2001-06-15 | 2001-08-22 | 김진경 | An utilization of the multi-follicular silver chips |
| KR100601306B1 (en) * | 2005-05-09 | 2006-07-13 | 주식회사 코오롱 | Artificial leather with excellent elasticity and its manufacturing method |
| JP6055702B2 (en) * | 2013-03-18 | 2016-12-27 | 株式会社クラレ | Artificial leather with silver, decorative molded body, and method for producing artificial leather with silver |
| JP6133088B2 (en) * | 2013-03-18 | 2017-05-24 | クラレプラスチックス株式会社 | Silver-like artificial leather and method for producing the same |
| CN117730180A (en) * | 2021-10-08 | 2024-03-19 | 世联株式会社 | Synthetic leather and skin materials |
| CN114921963B (en) * | 2022-04-29 | 2023-08-25 | 安安(中国)有限公司 | Production process of synthetic leather and metal hollowed-out synthetic leather |
-
1992
- 1992-12-25 JP JP4359255A patent/JP3059849B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06192966A (en) | 1994-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4018954A (en) | Sheet material | |
| KR100526910B1 (en) | Non-woven fabric and artificial leather | |
| US20060008631A1 (en) | Leather-like sheet and process for production thereof | |
| JP3059849B2 (en) | Artificial leather with silver | |
| JPH0397976A (en) | Artificial leather having excellent water vapor permeability and flexibility | |
| JPS635518B2 (en) | ||
| JP2003193377A (en) | Synthetic leather with three-dimensional effect and method for producing the same | |
| JPH03287880A (en) | Leather-like sheet material | |
| JPS6017871B2 (en) | Method for producing leather-like sheet material | |
| JPH01314789A (en) | Synthetic leather | |
| JP2001354899A (en) | Coated fabric and method for producing the same | |
| JP3009346B2 (en) | Leather-like sheet and method for producing the same | |
| JPH06294077A (en) | Synthetic leather and its production | |
| JPS63145489A (en) | Synthetic leather applicable with wrinkle like natural leather and production thereof | |
| JPH01266283A (en) | Leather-like sheet product and production thereof | |
| JP3076933B2 (en) | Suede-like fabric | |
| JPS6017872B2 (en) | Method for manufacturing leather-like sheet material | |
| JPS5933715B2 (en) | Method for producing leather-like sheet material with excellent three-dimensional appearance | |
| JPS6215673B2 (en) | ||
| JP2813410B2 (en) | Nubuck leather-like sheet | |
| JPH0860557A (en) | Leather-like sheet having nubuck-like appearance and its production | |
| JPH01246481A (en) | Production of thin layer microporous silvery surface with crimp | |
| KR100233214B1 (en) | Artificial leather containing skin layer and its process | |
| JPS605709B2 (en) | Method for producing leather-like sheets with excellent valley dyeing effect | |
| JPS5943588B2 (en) | Manufacturing method for high-quality leather-like sheets |