JPS648753B2 - - Google Patents
Info
- Publication number
- JPS648753B2 JPS648753B2 JP1304180A JP1304180A JPS648753B2 JP S648753 B2 JPS648753 B2 JP S648753B2 JP 1304180 A JP1304180 A JP 1304180A JP 1304180 A JP1304180 A JP 1304180A JP S648753 B2 JPS648753 B2 JP S648753B2
- Authority
- JP
- Japan
- Prior art keywords
- nonwoven web
- binder
- web
- artificial leather
- interlaced
- 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
Links
- 239000004744 fabric Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 32
- 239000002649 leather substitute Substances 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229920002994 synthetic fiber Polymers 0.000 claims description 12
- 239000012209 synthetic fiber Substances 0.000 claims description 12
- 239000002759 woven fabric Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000009499 grossing Methods 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 238000009940 knitting Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001410 Microfiber Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Description
【発明の詳細な説明】
本発明はスエード調人工皮革の製造方法に関す
るものであり、その目的とする処は強度、外観、
風合等のすべてにわたつてバランスよく優れたス
エード調人工皮革の製造方法を提供するにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing suede-like artificial leather, and its purpose is to improve strength, appearance,
To provide a method for manufacturing suede-like artificial leather that is well-balanced and excellent in all aspects such as texture.
本発明者等はさきにスエード調人工皮革の製造
方法の一方法であるプレボンド法について研究開
発を行つていた過程において得られた人工皮革に
おいて伸長時における残留歪が顕著に現われる欠
点が生ずることを知り、柔軟性、ドレープ性の付
与効果や外観を損うことなく、残留歪を可能な限
り低下せしめるべく鋭意研究の結果、合成繊維、
半合成繊維、天然繊維の単独あるいはこれらの混
合繊維で構成された不織ウエブを次の工程〜
によつて順次処理し、次いで工程処理面を研削
（Buffing）することを特徴とするスエード調人
工皮革の製造方法。 The present inventors previously discovered that the artificial leather obtained in the process of researching and developing the pre-bonding method, which is a method for manufacturing suede-like artificial leather, had the disadvantage of noticeable residual strain during elongation. As a result of intensive research to reduce residual strain as much as possible without impairing flexibility, drapability, or appearance, we have developed synthetic fibers.
The nonwoven web made of semi-synthetic fibers, natural fibers alone, or a mixture of these fibers is processed through the next process ~
1. A method for manufacturing suede-like artificial leather, characterized by sequentially treating the surface with the following steps: and then grinding (buffing) the process-treated surface.
不織ウエブの片面又は両面の平滑化を行う。 Smoothing is performed on one or both sides of the nonwoven web.
不織ウエブの平滑片面から当該不織ウエブ厚
さの10％〜50％の浸透深度をもつて結合剤(A)を
浸透固着させる。 The binder (A) is penetrated and fixed from one smooth side of the nonwoven web to a penetration depth of 10% to 50% of the thickness of the nonwoven web.
により得られた不織ウエブの残存空隙内に
樹脂成分(B)を浸透固着させる。 The resin component (B) is infiltrated and fixed into the remaining voids of the nonwoven web obtained by the above steps.
結合剤(A)は溶解するが不織ウエブの構成繊維
および樹脂成分(B)は溶解しない溶剤で結合剤(A)
を溶解除去し、次いで乾燥する。 The binder (A) is used in a solvent that dissolves the binder (A) but does not dissolve the constituent fibers and resin components (B) of the nonwoven web.
is dissolved and removed, and then dried.
を発明し特願昭54−139960号として出願された。was invented and filed as Japanese Patent Application No. 139960/1983.
これによれば目的とする残留歪の低下は一応達
することが出来たが、全体としての強度、外観、
風合等にわたつてバランスのよい優れたスエード
調の人工皮革としては今一歩という感じであつ
て、これがため、本発明者等は前記した発明をよ
り改良し、全体としての強度、外観、風合等、す
べてにわたつてバランスよく優れたものを得るべ
く鋭意研究し実験を重ねた結果、熱可塑性合成繊
維からなる不織ウエブ２枚の間に、編物または織
物を、挿入したものであつて、かつ前記不織ウエ
ブの全重量(A)と前記編物または織物の重量(B)の比
（Ａ／Ｂ）が1.3以上であるものを、これら不織ウ
エブと編物または織物とを互いに交絡せしめて交
絡不織ウエブとなし、この交絡不織ウエブを次に
示す(A)〜(D)の工程
(A) 交絡不織ウエブの厚みよりも狭く、かつ交絡
不織ウエブの厚みの1/10よりも広い間隙であつ
て、しかも交絡不織ウエブの上下両面が接すべ
き面が80℃以上に加熱された間隙を、前記交絡
不織ウエブを通過させて、この交絡不織ウエブ
の両面を平滑化させる工程
(B) 交絡不織ウエブの平滑化した両面のうちの片
面から、平滑化した交絡不織ウエブの厚さの10
〜50％の深さまで結合剤を浸透固化させる工程
(c) 結合剤が浸透固化した交絡不織ウエブの残存
空隙内に弾性高分子物質を充填固着させる工程
(D) 結合剤は溶解するが、弾性高分子物質は溶解
しない溶剤で、前記工程(B)で得た交絡不織ウエ
ブ中の結合剤を溶解除去する工程
をその順序で処理した後、前記工程(B)において結
合剤を浸透せしめた面を研削（Buffing）するこ
とを特徴とするスエード調人工皮革の製造方法を
得たもので、この本発明の方法は、前記した特願
昭54−139960号の発明を種々の点で改良した発明
であるが、その主な改良点の第１は素材とする不
織ウエブが先の発明にあつては合成繊維、半合成
繊維、天然繊維の単独あるいはこれらの混合繊維
で構成された不織ウエブであるのに対し、本発明
にあつては熱可塑性合成繊維からなる不織ウエブ
２枚の間に、編物または織物（以下単に編織物と
いう）が挿入されたもの、即ち編織物を中にして
その両面に熱可塑性合成繊維の不織ウエブが重ね
合された三層のサンドイツチ構造となつているも
ので、しかも、この不織ウエブの全重量と、編織
物の重量との比が1.3以上であるように配分され
ていなければならないものであり、更に不織ウエ
ブと編織物とは不織ウエブの構成繊維が交絡して
不織ウエブと編織物及び不織ウエブとが交絡して
三層は一体化された交絡不織ウエブとされなけれ
ばならないものである。 According to this, we were able to achieve the desired reduction in residual strain, but the overall strength, appearance,
This is a step forward in terms of excellent suede-like artificial leather with a well-balanced feel, etc. Therefore, the present inventors have further improved the above-mentioned invention to improve its overall strength, appearance, and wind. As a result of intensive research and repeated experiments to obtain a well-balanced and excellent product in all cases, we have found that a knitted or woven fabric is inserted between two nonwoven webs made of thermoplastic synthetic fibers. , and the ratio (A/B) of the total weight (A) of the nonwoven web to the weight (B) of the knitted fabric or woven fabric is 1.3 or more, and the nonwoven web and the knitted fabric or woven fabric are intertwined with each other. This interlaced non-woven web is then processed through the following steps (A) to (D) to form an interwoven non-woven web that is narrower than the thickness of the inter-woven non-woven web and 1/10 of the thickness of the inter-woven non-woven web. The interlaced nonwoven web is passed through a gap that is wider than the above, and in which the surface where the upper and lower surfaces of the interwoven nonwoven web should be in contact is heated to 80°C or higher, and both sides of the interlaced nonwoven web are heated. Smoothing step (B) From one side of the smoothed both sides of the entangled nonwoven web, 10 of the thickness of the smoothed entangled nonwoven web
A process of penetrating and solidifying the binder to a depth of ~50% (c) A process of filling and fixing an elastic polymer substance into the remaining voids of the intertwined nonwoven web in which the binder has permeated and solidified (D) The binder dissolves, but After performing the steps of dissolving and removing the binder in the entangled nonwoven web obtained in step (B) in that order using a solvent that does not dissolve the elastic polymer material, the binder is infiltrated in step (B). The method of the present invention improves the invention of the above-mentioned Japanese Patent Application No. 139960-1980 in various respects. However, the first major improvement is that the nonwoven web used as the raw material is a nonwoven web made of synthetic fibers, semi-synthetic fibers, natural fibers alone or a mixture of these fibers in the previous invention. In contrast to the woven web, in the present invention, a knitted fabric or woven fabric (hereinafter simply referred to as a knitted fabric) is inserted between two nonwoven webs made of thermoplastic synthetic fibers, that is, a knitted fabric is used as the middle. It has a three-layer sandwich structure in which a non-woven web of thermoplastic synthetic fibers is superimposed on both sides, and the ratio of the total weight of this non-woven web to the weight of the knitted fabric is 1.3. The nonwoven web and the knitted fabric must be distributed in such a way that the constituent fibers of the nonwoven web are intertwined, and the nonwoven web, knitted fabric, and nonwoven web are intertwined. The layers must be integrated into an interlaced nonwoven web.
また第２の点はこのようにして構成された交絡
不織ウエブの両面を平滑化させるのであるが、こ
の平滑化は加熱間隙を通過させることによつて平
滑化されるものであり、この間隙は、交絡不織ウ
エブの厚みよりも狭く、かつ交絡不織ウエブの厚
みの1/10よりも広い間隙でなければならず、しか
も、交絡不織ウエブの上下両面が接すべき面が80
℃以上に加熱された間隙を通過させなければなら
ないことである。 The second point is to smooth both sides of the interlaced nonwoven web constructed in this way, but this smoothing is done by passing it through a heated gap, and this smoothing is done by passing it through a heated gap. The gap must be narrower than the thickness of the interlaced nonwoven web and wider than 1/10 of the thickness of the interwoven nonwoven web, and the surface where the upper and lower surfaces of the interlaced nonwoven web should be in contact must be 80
It must pass through a gap that is heated to temperatures above ℃.
主としてこのように改良された前記製造方法に
従うことによつて柔軟性、ドレープ性は勿論良好
であり、残留歪も殆んどなく、強度、外観、風合
等、スエード調人工皮革に具備すべき要件がバラ
ンス良く極めて優秀に保持する製品を得たもので
ある。 Mainly by following the above-mentioned manufacturing method improved in this way, the flexibility and drapability are of course good, there is almost no residual distortion, and the strength, appearance, texture, etc. that suede-like artificial leather should have. We have obtained a product that meets the requirements in a well-balanced manner and holds it extremely well.
本発明にあつては不織ウエブを構成する熱可塑
性合成繊維は例えばポリエステル、ポリアミド、
ポリオレフイン、ポリアクリロニトリル、ポリビ
ニルアルコール、ポリ塩化ビニル等の重合体或は
上記重合体を主成分とする共重合体又は重合体混
合物等からなる繊維をその一例とし、熱可塑性繊
維である限り何等限定されるものではない。また
この熱可塑性合成繊維を得るには如何なる製造法
によつても良いが、使用する不織ウエブが長繊維
の集合体である不織ウエブか、或は短繊維の集合
体である不織ウエブであるかによつて異なり、そ
れぞれ好ましい方法によつて得ればよいが、単繊
維の平均直径が8μ以下の極細繊維の不織ウエブ
を得るには溶融紡糸の可能な合成高分子からメル
トブローイング法によつて得ることは好ましい。
また不織ウエブを得るには例えば通常の方法でス
テープルフアイバーを得、これをカード及びクロ
スラツパーを用いてウエブにするとか、前記した
メルトブローイング法によるとか、或は長繊維の
集合体としての不織ウエブを得る任意の方法によ
る等、長繊維、短繊維の別に応じて任意の方法に
よればよい。 In the present invention, the thermoplastic synthetic fibers constituting the nonwoven web are, for example, polyester, polyamide,
Examples include fibers made of polymers such as polyolefin, polyacrylonitrile, polyvinyl alcohol, and polyvinyl chloride, or copolymers or polymer mixtures containing the above polymers as main components, and there are no limitations as long as they are thermoplastic fibers. It's not something you can do. Furthermore, any manufacturing method may be used to obtain this thermoplastic synthetic fiber, but the nonwoven web used may be a nonwoven web that is an aggregate of long fibers or a nonwoven web that is an aggregate of short fibers. It depends on the type of fiber, and it can be obtained by a preferred method, but in order to obtain a nonwoven web of ultrafine fibers with an average diameter of 8μ or less, melt blowing from a synthetic polymer that can be melt spun is used. Obtaining by method is preferred.
In addition, in order to obtain a nonwoven web, for example, staple fibers are obtained by a conventional method and then made into a web using a card and a cross wrapper, by the melt blowing method described above, or by forming a nonwoven web as an aggregate of long fibers. Any method may be used depending on whether long fibers or short fibers are used, such as any method for obtaining a web.
本発明で用いられる編織物は各種の編物や織物
を用いることが出来、特別に限定されるものはな
く、目的とする人工皮革の風合、強度その他の条
件に適合するよう任意に選定すればよく、またこ
れらの編物や織物に用いられる糸の種類、太さ、
組織等にあつても何等特別に限定されることはな
い。 The knitted fabric used in the present invention can be made of various knitted fabrics or woven fabrics, and is not particularly limited, and can be arbitrarily selected to suit the texture, strength, and other conditions of the desired artificial leather. Also, the type, thickness, and type of yarn used in these knitting and woven fabrics.
There are no particular limitations regarding organizations, etc.
本発明で用いられる結合剤としては例えばデキ
ストリン、デンプン、カルボキシルメチルセルロ
ーズ、メチルセルローズ、カゼイン、ポリエチレ
ンオキサイド、ポリビニルアルコール、ポリ塩化
ビニル、ポリ酢酸ビニル、その他各種合成樹脂、
天然樹脂、の単独または２種以上の組み合せから
なるものが挙げられるが、注意しなければならな
いのは、この結合剤が与えられた後に、弾性高分
子物質が附与されるが、この弾性高分子物質の溶
剤と相溶性を有するものは結合剤として用いるこ
とは適当でない。そしてこの結合剤の不織ウエブ
への浸透固着は結合剤の溶液、エマルジヨン、分
散物等をコーテイング方法例えばドクターナイフ
コーテイング、ロールコーテイング等の方法で不
織ウエブに浸透される。 Examples of the binder used in the present invention include dextrin, starch, carboxylmethylcellulose, methylcellulose, casein, polyethylene oxide, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, and various other synthetic resins.
Natural resins may be used alone or in combination of two or more types, but care must be taken that after this binder is applied, an elastic polymer substance is added, but this elastic polymer Molecular substances that are compatible with the solvent are not suitable for use as binders. In order to penetrate and fix the binder into the nonwoven web, the nonwoven web is penetrated by a coating method such as doctor knife coating, roll coating, etc. with a solution, emulsion, dispersion, etc. of the binder.
本発明で用いられる弾性高分子物質としてはポ
リ塩化ビニル、ポリ酢酸ビニル、ポリアミド、ポ
リエステル、ポリアクリレート、ポリウレタン、
各種合成ゴム等の単独または２種以上の組み合せ
を挙げることができ、これらを不織ウエブに充填
させるには、これら弾性高分子物質の溶液、エマ
ルジヨン、分散物の形として含浸操作によつて行
われる。 Elastic polymer materials used in the present invention include polyvinyl chloride, polyvinyl acetate, polyamide, polyester, polyacrylate, polyurethane,
Various types of synthetic rubbers can be used alone or in combination of two or more types, and in order to fill the nonwoven web with these, it is carried out by an impregnation operation in the form of a solution, emulsion, or dispersion of these elastic polymer substances. be exposed.
この時に用いられる弾性高分子物質の溶剤或は
分散媒は、前記した結合剤や不織ウエブの構成繊
維を溶解ないし膨潤するものであつてはならな
い。 The solvent or dispersion medium for the elastic polymer material used at this time must not dissolve or swell the binder or the constituent fibers of the nonwoven web.
本発明で用いられる交絡不織ウエブは２枚の不
織ウエブの間に編織物が挿入されているものであ
るがこれは編織物の挿入、或は不織ウエブと編織
物との重ね合せ等の手段によつて限定されるもの
ではなく、編織物の両面に不織ウエブが存在する
状態或は、不織ウエブの中間に編織物が埋設存在
する等の如き状態を意味するものである。 The intertwined nonwoven web used in the present invention is one in which a knitted fabric is inserted between two nonwoven webs, and this can be done by inserting a knitted fabric, or by overlapping a nonwoven web and a knitted fabric, etc. The present invention is not limited by the means used, but refers to a state in which nonwoven webs are present on both sides of a knitted fabric, or a state in which a knitted fabric is embedded in the middle of a nonwoven web.
本発明で用いられる不織ウエブの単繊維の繊度
は、編織物の両面にある両方の不織ウエブが同じ
繊度のものであつてもよいことは勿論、互に異な
る繊度のものであつても差支えなく、例えば単繊
維の平均直径が8μ以下の如き極細繊維の場合に
はその差は３〜6μ程度が好ましい。 Regarding the fineness of the single fibers of the nonwoven web used in the present invention, both nonwoven webs on both sides of the knitted fabric may have the same fineness, or they may have different finenesses. There is no problem; for example, in the case of ultrafine fibers such as single fibers having an average diameter of 8 microns or less, the difference is preferably about 3 to 6 microns.
本発明にあつては交絡不織ウエブは２枚の不織
ウエブの間に編織物が存在しなければならない
が、このように三層構造とするのは人工皮革とし
ての強度を保持する上に必要なことであり、また
不織ウエブの重量と編織物の全重量との比が1.3
以上なければならないが、これは表面の平滑を優
良にし、天然皮革様のソフトな風合を有せしめる
上で必要なことであつて、この比が1.3以下であ
ると平滑性が悪くなり、ドレープ性に劣るものと
なり極端には皮革様の感じから織物様の風合に近
づいて好ましくない。 In the present invention, the interlaced nonwoven web must have a knitted fabric between two nonwoven webs, but the three-layer structure is designed to maintain the strength as an artificial leather and to maintain the strength of the artificial leather. It is necessary and also that the ratio of the weight of the nonwoven web to the total weight of the knitted fabric is 1.3.
This ratio is necessary in order to make the surface smooth and have a soft texture similar to natural leather. If this ratio is less than 1.3, the smoothness will deteriorate and the drapery will deteriorate. The texture is inferior, and in the extreme, the texture changes from leather-like to textile-like, which is undesirable.
更に不織ウエブと編織物との間、更に詳しくは
両側の不織ウエブ同志や、両側の不織ウエブと編
織物とは交絡されて一体化されていなければなら
ないが、これにはニードルパンチングを施すこと
によつて得られるが、これには片側からのパンチ
ングであつても、両側からのパンチングあつても
差支えなく、３層が一体化されればよい。 Furthermore, the nonwoven web and the knitted fabric, more specifically, the nonwoven webs on both sides, and the nonwoven web and the knitted fabric on both sides must be intertwined and integrated, which requires needle punching. This can be achieved by punching from one side or from both sides, as long as the three layers are integrated.
本発明にあつてはこのようにして得られた交絡
不織ウエブは、加熱された間隙を通過させられて
その両面に平滑性が与えられるのであるが、この
間隙は交絡不織ウエブの厚さよりも狭く、かつ交
絡不織ウエブの厚みの1/10よりも広い間隙である
ことが必要であつて、これは得られた人工皮革に
好ましい平滑さを与えるために必要である。 In the present invention, the interlaced nonwoven web thus obtained is passed through a heated gap to impart smoothness to both sides, but this gap is larger than the thickness of the interlaced nonwoven web. It is necessary that the gap be narrow and wider than 1/10 of the thickness of the interlaced nonwoven web, which is necessary in order to give the resulting artificial leather a desirable smoothness.
この間隙が交絡不織ウエブの厚みより広ければ
平滑さを与えることは出来ず、また交絡不織ウエ
ブの厚みの1/10よりも狭い間隙にすると、僅から
ウエブの密度斑や、編織物の編目、織目の影響が
出て、むしろ凹凸が生ずることとなり平滑さを損
うこととなる。これと共に、この間隙は80℃以上
に加熱されていなければならないがこれは、前記
した間隙の広さとも関連して加熱によつてウエブ
の厚み方向の繊維の密度勾配を適当に調整する役
割を果たし、緻密化と平滑さとを得るために必要
であつて、80℃以下であつては望ましい繊維の密
度勾配が得られず、その結果として緻密さと平滑
さが得られない。またこの加熱は交絡不織ウエブ
の両面に与えられなければならないから、交絡不
織ウエブの接すべき間隙の２面は加熱されていな
ければならず、もし片面だけの加熱であつては加
熱されたウエブの面の密度が密になり、これに反
して非加熱のウエブの面の密度はそのまゝの状態
であるため、シートの厚み方向に密度の差がつき
すぎて好ましいシートが得られず、また非加熱面
での平滑性が得られない。 If this gap is wider than the thickness of the interlaced nonwoven web, it will not be possible to provide smoothness, and if the gap is narrower than 1/10 of the thickness of the interlaced nonwoven web, there will be slight density unevenness in the web or in the knitted fabric. The influence of the stitches and textures will appear, causing unevenness and impairing the smoothness. At the same time, this gap must be heated to a temperature of 80°C or higher, which also plays a role in appropriately adjusting the fiber density gradient in the thickness direction of the web by heating, which is related to the width of the gap mentioned above. However, if the temperature is below 80°C, which is necessary to obtain densification and smoothness, the desired fiber density gradient cannot be obtained, and as a result, densification and smoothness cannot be obtained. Also, since this heating must be applied to both sides of the interlaced nonwoven web, the two sides of the interlaced nonwoven web in the gap that should be in contact must be heated, and if only one side is heated, it will not be heated. The surface density of the heated web becomes denser, whereas the surface density of the non-heated web remains the same, so there is too much difference in density in the thickness direction of the sheet, making it difficult to obtain a desirable sheet. Moreover, smoothness cannot be obtained on the non-heated surface.
なお、この間隙の加熱温度は80℃以上を必要と
するが好ましくは100℃以上でありこの間隙を通
る際、交絡不織ウエブに水分を与えて通過させる
ことによつて、その効果は更に増加される場合も
ある。 The heating temperature in this gap needs to be 80℃ or higher, but preferably 100℃ or higher, and the effect is further increased by adding moisture to the intertwined nonwoven web when passing through this gap. In some cases, it may be done.
この間隙とは例えば所定の間隙を置いて設けら
れた２本の加熱ロールによつて間隙が構成される
が、これらの加熱ロールが回転するか否かは格別
に制限されない。 This gap is, for example, a gap formed by two heating rolls provided with a predetermined gap, but there is no particular restriction on whether or not these heating rolls rotate.
また所定の間隔を置いて平行に設けられた２枚
の加熱板によつても間隙が構成されるが、本発明
にあつては間隙とは、これらに限られることな
く、本発明の精神を逸脱しない限り如何なる構成
のものであつてもよい。上記した間隙についての
説明は便宜上、間隙としての距離、或は間隔と、
間隙の加熱とを区別して説明したが、加熱された
間隙を通る際に交絡不織ウエブに与えられる作用
は圧力と熱との相乗作用とも言うべきものであつ
て、これらの相乗効果によつて平滑さが格段と向
上したものである。 A gap may also be formed by two heating plates placed in parallel with a predetermined spacing, but in the present invention, the gap is not limited to this, and the spirit of the present invention is not limited to this. Any configuration may be used as long as it does not deviate. For convenience, the above explanation of the gap is based on the distance or interval as the gap,
Although the explanation has been made by distinguishing between the heating of the gap, the action given to the entangled nonwoven web when passing through the heated gap can be called a synergistic effect of pressure and heat, and due to these synergistic effects, The smoothness has been greatly improved.
たゞ注意しなければならないのは平滑さについ
て言うならば、平滑さの格段の向上は、前記した
不織ウエブの重量と編織物の重量との比が1.3以
上であつて、編織物の両側に不織ウエブが三層構
造となつた交絡不織ウエブを用いてしかも、前記
した加熱間隙を通過させるためであつて、そのい
ずれかを欠いてもその効果は期待できない。 Regarding smoothness, it is important to note that a significant improvement in smoothness occurs when the ratio of the weight of the nonwoven web to the weight of the knitted fabric is 1.3 or more, and both sides of the knitted fabric are This is because an intertwined nonwoven web having a three-layer structure is used and the nonwoven web is passed through the heating gap described above, and the effect cannot be expected even if any one of them is missing.
本発明は上記した如く特定した交絡不織ウエブ
を特定した平滑化処理工程を経させることによつ
て交絡不織ウエブに人工皮革として好ましき性状
を付与し、以後の特定の処理工程と相まつて極め
て優れた人工皮革を得るものであり、以下更に詳
細に説明すると、上記した通りにして得られた交
絡不織ウエブの片面から、このウエブに結合剤が
コーテイングして与えられるが、この片面からの
結合剤の付与は、天然皮革様のソフトな風合とな
し、残留歪を減少させると共に適度に長い毛足と
なさしめ、しかもフインガーマークの画き易い表
面効果を与える点で必要である。この時、この結
合剤の浸透深度（浸透厚／交絡不織ウエブ厚×
100）を10〜50％としなければならないが、この
浸透深度は10％以下であると柔軟性、ドレープ性
の効果が不充分であり、50％を超える場合には残
留歪が大きく現われる。 The present invention imparts desirable properties as artificial leather to the interlaced nonwoven web by subjecting the specified interlaced nonwoven web to a specified smoothing treatment step as described above, which is combined with the subsequent specific treatment steps. In the following, it will be explained in more detail that one side of the interlaced nonwoven web obtained as described above is coated with a binder. The application of a binder from the above is necessary in order to create a soft texture similar to natural leather, reduce residual distortion, create appropriately long piles, and provide a surface effect that makes it easy to draw finger marks. . At this time, the penetration depth of this binder (penetration thickness/entangled nonwoven web thickness x
100) must be 10 to 50%, but if the penetration depth is less than 10%, the effects of flexibility and drapability will be insufficient, and if it exceeds 50%, large residual strains will appear.
またこの結合剤を、片面（例えば上面）から浸
透させた場合、この結合剤は上面の不織ウエブの
全面に浸透し、更にこの上面の不織ウエブに接し
て位置する編織物をも浸透し、この編織物の下面
の不織ウエブとの境界まで浸透固化させることに
よつて、弾性高分子物質を含浸させた時、編織物
の埋設箇所において交絡している繊維に、前記し
た弾性高分子物質が直接付着することがないか
ら、これによつて得られた人工皮革の曲げ特性が
良好になつて風合がソフトになるものである。 Furthermore, when this binder is infiltrated from one side (for example, the top side), this binder permeates the entire surface of the top nonwoven web, and further penetrates the knitted fabric located in contact with the top nonwoven web. When the elastic polymer material is impregnated by penetrating and solidifying the lower surface of the knitted fabric up to the boundary with the non-woven web, the elastic polymer Since no substances are directly attached, the resulting artificial leather has good bending properties and a soft feel.
この様にして結合剤が浸透固化した交絡不織ウ
エブの残存空隙内に弾性高分子物質を充填固着さ
せ、その後、前記の結合剤を溶解除去し、更に前
記した結合剤を浸透せしめた面を研削
（Buffing）することによつてスエード調人工皮
革が得られるが、この時、単繊維の平均直径が
8μ以下の極細繊維からなる不織ウエブを用いる
ことによつてより一層天然皮革に酷似したソフト
な風合をもち、フインガーマークが極めて好まし
く画ける人工皮革を得ることができる。 In this way, an elastic polymer substance is filled and fixed in the remaining voids of the entangled nonwoven web in which the binder has permeated and hardened, and then the binder is dissolved and removed, and the surface impregnated with the binder is Suede-like artificial leather can be obtained by grinding (buffing), but at this time, the average diameter of the single fibers is
By using a nonwoven web made of ultrafine fibers of 8 μm or less, it is possible to obtain artificial leather that has a soft texture that closely resembles natural leather, and that has extremely favorable finger marks.
本発明は上記した如くに、特定した交絡不織ウ
エブ即ち熱可塑性合成繊維からなる不織ウエブ２
枚の間に編織物を、不織ウエブの重量と編織物の
重量との比が1.3以上であるように挿入したもの
を、これら不織ウエブ同志及び不織ウエブと編織
物とを交絡させた交絡不織ウエブを用い、これを
特定の平滑化付与工程、即ち、交絡不織ウエブの
厚みより狭く、かつ交絡不織ウエブの厚みの1/10
よりも広い間隙であつて、しかも交絡不織ウエブ
の上下両面が接すべき面が80℃以上に加熱された
間隙を、前記交絡不織ウエブを通過させて両面を
平滑化させる工程を経させて、交絡不織ウエブに
好ましき特性を付与し、以後引続いてこの交絡不
織ウエブの片面から、この平滑化したウエブの厚
さの10〜50％の深さまで結合剤を浸透固化させる
工程とついでこのウエブの残存空隙内に弾性高分
子物質を浸透固着させる工程と、更には前記結合
剤を溶解除去する工程とを経て、結合剤の浸透せ
しめられた面を研削（Buffing）することによつ
て、さきに発明した製造法に依つては未だ充分に
は得られなかつた強度、外観風合のすべてにわた
つてバランスよく極めて優れたスエード調人工皮
革を得ることが出来たものである。 As described above, the present invention provides a specified intertwined nonwoven web, that is, a nonwoven web 2 made of thermoplastic synthetic fibers.
A knitted fabric is inserted between the sheets so that the ratio of the weight of the nonwoven web to the weight of the knitted fabric is 1.3 or more, and these nonwoven webs and the nonwoven web and the knitted fabric are entangled. An interlaced non-woven web is used, which is subjected to a specific smoothing process, i.e. narrower than the thickness of the entangled non-woven web and 1/10 of the thickness of the entangled non-woven web.
The interlaced nonwoven web is passed through a gap that is wider than the above gap, and in which the surfaces where the upper and lower surfaces of the interlaced nonwoven web are to be in contact are heated to 80° C. or higher to undergo a step of smoothing both sides. to impart desirable properties to the entangled nonwoven web, and subsequently penetrate and solidify the binder from one side of the entangled nonwoven web to a depth of 10 to 50% of the thickness of the smoothed web. Then, through a step of infiltrating and fixing an elastic polymer substance into the remaining voids of this web, and further a step of dissolving and removing the binder, the surface impregnated with the binder is ground (buffed). As a result, we were able to obtain suede-like artificial leather that was well-balanced and excellent in terms of strength, appearance, and texture, which had not yet been achieved using the previously invented manufacturing method. .
実施例
単繊維の平均直径が3.0μの６−ナイロン繊維か
らなるメルトブローイング法で作成した目付120
ｇ／m2の不織ウエブと、これと同径で同様の方法
で作成した160ｇ／m2の不織ウエブ２枚の間に、
糸遺いが30d／6fで、編組織がトリコツトハーフ
であり、編密度は28ゲージであり目付が60ｇ／m2
のナイロントリコツトを重ね合せて、これに両側
からパンチ密度が900パンチ／cm2のニードルパン
チングを施し、厚さ1.9mmの交絡不織ウエブを得
た。この交絡不織ウエブを構成する不織ウエブの
全重量Ａとナイロントリコツトの重量Ｂの比Ａ／
Ｂは120ｇ＋160ｇ／60ｇ＝4.66となるこの交絡不
織ウエブを、間隙が0.9mmに設定されて、170℃に
加熱された２本の回転金属ロールの間隙を、通過
速度2.5ｍ／minで通過させて厚さ1.15mm、320
ｇ／m2の交絡不織ウエブとなつた。次にポリビニ
ルアルコールの６％水溶液（粘度2000CP）をこ
の交絡不織ウエブの目付120ｇ／m2のウエブ側に
ドクターナイフによつて付着量が15ｇ／m2となる
ようにコーテイングし、30秒間放置してから乾燥
させた。この時の浸透深度は0.5mmであつて、前
記加熱ロールを通過した後のウエブの厚みに対し
ては42％となり、ナイロントリコツトの下部まで
浸透していた。Example Fabric weight 120 made by melt blowing method consisting of 6-nylon fibers with an average diameter of 3.0μ
g/m 2 nonwoven web and two 160 g/m 2 nonwoven webs with the same diameter and made in the same way,
The yarn weight is 30d/6f, the knitting structure is tricotto half, the knitting density is 28 gauge, and the basis weight is 60g/m 2
Nylon tricots were layered together and needle punched from both sides at a punch density of 900 punches/cm 2 to obtain an interlaced nonwoven web with a thickness of 1.9 mm. The ratio A/
B is 120g + 160g / 60g = 4.66 This intertwined nonwoven web is passed through the gap between two rotating metal rolls heated to 170°C with a gap of 0.9mm at a passing speed of 2.5m/min. Thickness 1.15mm, 320
g/m 2 interlaced nonwoven web. Next, a 6% aqueous solution of polyvinyl alcohol (viscosity 2000CP) was coated on the web side of the entangled nonwoven web with a basis weight of 120 g/m 2 using a doctor knife so that the adhesion amount was 15 g/m 2 and left for 30 seconds. Then it was dried. The penetration depth at this time was 0.5 mm, which was 42% of the thickness of the web after passing through the heating roll, and it penetrated to the bottom of the nylon tricot.
次に、このポリビニルアルコールが浸透固化し
た交絡不織ウエブに、エーテル系ポリウレタンエ
ラストマーの８％ジメチルホルムアミド溶液を含
浸させて、この溶液の付着量が980ｇ／m2となる
ように金属ロールで絞り、直ちに水中に浸漬して
凝固させ、更に60℃の温水中でポリビニルアルコ
ールを充分溶解除去した後乾燥し、前記ポリビニ
ルアルコール処理面を＃100サンドペーパーによ
るバフ起毛を行つてスエード調人工皮革を得た。 Next, the interlaced nonwoven web in which the polyvinyl alcohol has permeated and solidified is impregnated with an 8% dimethylformamide solution of an ether-based polyurethane elastomer, and squeezed with a metal roll so that the amount of the solution adhered is 980 g/ m2 . It was immediately immersed in water to coagulate, and the polyvinyl alcohol was sufficiently dissolved and removed in warm water at 60°C, then dried, and the polyvinyl alcohol treated surface was buffed with #100 sandpaper to obtain suede-like artificial leather. .
このものは強度、外観、風合のすべてにわたつ
てバランスのよい極めてすぐれたスエード調人工
皮革であつた。 This product was an excellent suede-like artificial leather with a good balance in terms of strength, appearance, and texture.
実施例
単繊維の平均直径が4.0μの６−ナイロン繊維か
らなるメルトブローイング法で作成した目付150
ｇ／m2の不織ウエブ２枚の間に、糸遺いが20d／
1f、編組織がトリコツトハーフ、編密度が28ゲー
ジであり目付が40ｇ／m2のナイロントリコツトを
挿入重ね合せ、これに両側からパンチ密度900パ
ンチ／cm2のニードルパンチングを施し、厚さ1.8
mmの交絡不織ウエブを得た。この交絡不織ウエブ
を構成する不織ウエブの全重量Ａとナイロントリ
コツトの重量Ｂの比Ａ／Ｂは150×２／40＝7.5と
なるこの交絡不織ウエブを間隙が0.9mmに設定さ
れて、170℃に加熱された２本の回転金属ロール
の間隙を通過速度2.5ｍ／minで通過させて厚さ
1.20mm345ｇ／m2の交絡不織ウエブとなつた。Example Fabric weight 150 made by melt blowing method consisting of 6-nylon fibers with an average diameter of 4.0μ
Between two sheets of g/m 2 nonwoven web, 20 d/m of thread is left.
1F, the knitting structure is tricot half, the knitting density is 28 gauge, and the fabric weight is 40 g/m 2 Nylon tricot is inserted and overlapped, and this is needle punched from both sides with a punch density of 900 punches/cm 2 , and the thickness is 1.8
An interlaced nonwoven web of mm was obtained. The ratio A/B of the total weight A of the nonwoven web constituting this interwoven nonwoven web and the weight B of the nylon tricot is 150 x 2/40 = 7.5.The interlaced nonwoven web is set at a gap of 0.9 mm. The thickness was
The result was an interlaced nonwoven web of 1.20 mm and 345 g/m 2 .
次にポリビニルアルコールの10％水溶液（粘度
4600CP）をドクターナイフによつて付着量が12
ｇ／m2となるように交絡不織ウエブの片面にコー
テイングし、30秒間放置してから乾燥させた。こ
の時の浸透深度は0.24mmであつて、前記加熱ロー
ルを通過した後のウエブの厚みに対しては20％で
あり、ナイロントリコツトは塗布表面から0.6mm
の位置にあるため、ポリビニルアルコール水溶液
は浸透しなかつた。次にこのポリビニルアルコー
ルが浸透固化した交絡不織ウエブに、エーテル系
ポリウレタンエラストマーの８％ジメチルホルム
アミド溶液を含浸させてこの溶液の付着量が1050
ｇ／m2となるように金属ロールで絞り、直ちに水
中に浸漬して凝固させ、更に60℃の温水中でポリ
ビニルアルコールを充分溶解除去した後、乾燥
し、前記ポリビニルアルコール処理面を＃100サ
ンドペーパーによるバフ起毛を行つてスエード調
人工皮革を得た。 Next, a 10% aqueous solution of polyvinyl alcohol (viscosity
4600CP) with a doctor knife to a coating amount of 12
g/m 2 on one side of the interlaced nonwoven web and allowed to stand for 30 seconds before drying. The penetration depth at this time is 0.24 mm, which is 20% of the thickness of the web after passing through the heating roll, and the nylon tricot is 0.6 mm from the coating surface.
, the polyvinyl alcohol aqueous solution did not penetrate. Next, the entangled nonwoven web in which the polyvinyl alcohol has permeated and solidified is impregnated with an 8% dimethylformamide solution of ether polyurethane elastomer, and the amount of adhesion of this solution is 1050.
g/ m2 , squeezed with a metal roll, immediately immersed in water to solidify, thoroughly dissolved and removed polyvinyl alcohol in 60°C warm water, dried, and sanded the polyvinyl alcohol-treated surface with #100 sand. A suede-like artificial leather was obtained by buffing with paper.
このものは前記実施例によつて得たと同様の
強度、外観、風合を有するすぐれたものであるが
特にドレープ性とフインガーマーク性とにあつて
は実施例によるものより優れたものとなつた。 This product has excellent strength, appearance, and texture similar to those obtained in the above example, but is particularly superior to the product in the example in terms of drapability and finger mark properties. Ta.
Claims (1)
間に、編物または織物を挿入したものであつて、
かつ前記不織ウエブの全重量(A)と前記編物または
織物の重量(B)の比（Ａ／Ｂ）が1.3以上であるも
のを、これら不織ウエブと編物または織物とを互
いに交絡せしめて交絡不織ウエブとなし、この交
絡不織ウエブを次に示す(A)〜(D)の工程 (A) 交絡不織ウエブの厚みよりも狭く、かつ交絡
不織ウエブの厚みの1/10よりも広い間〓であつ
て、しかも交絡不織ウエブの上下両面が接すべ
き面が80℃以上に加熱された間〓を、前記交絡
不織ウエブを通過させて、この交絡不織ウエブ
の両面を平滑化させる工程 (B) 交絡不織ウエブの平滑化した両面のうちの片
面から、平滑化した交絡不織ウエブの厚さの10
〜50％の深さまで結合剤を浸透固化させる工程 (C) 結合剤が浸透固化した交絡不織ウエブの残存
空〓内に弾性高分子物質を充填固着させる工程 (D) 結合剤は溶解するが、弾性高分子物質は溶解
しない溶剤で、前記工程(B)で得た交絡不織ウエ
ブ中の結合剤を溶解除去する工程 をその順序で処理した後、前記工程(B)において結
合剤を浸透せしめた面を研削（Buffing）するこ
とを特徴とするウエード調人工皮革の製造方法。 ２ 不織ウエブの１枚と他の１枚の不織ウエブは
その不織ウエブを構成する繊維の単繊維繊度が異
なることを特徴とする特許請求の範囲第１項記載
のスエード調人工皮革の製造方法。 ３ 不織ウエブを構成する熱可塑性合成繊維の単
繊維の平均直径が8μ以下であることを特徴とす
る特許請求の範囲第１項又は第２項記載のスエー
ド調人工皮革の製造方法。 ４ 不織ウエブはメルトブローイング法によつて
得られた不織ウエブであることを特徴とする特許
請求の範囲第１項又は第２項又は第３項記載のス
エード調人工皮革の製造方法。 ５ 結合剤は編物または織物に浸透していること
を特徴とする特許請求の範囲第１項又は第２項又
は第３項又は第４項記載のスエード調人工皮革の
製造方法。 ６ 結合剤は編物または織物に浸透していないこ
とを特徴とする特許請求の範囲第１項または第２
項又は第３項又は第４項記載のスエード調人工皮
革の製造方法。[Scope of Claims] 1 A knitted or woven fabric inserted between two nonwoven webs made of thermoplastic synthetic fibers,
and the ratio (A/B) of the total weight (A) of the nonwoven web to the weight (B) of the knitted fabric or woven fabric is 1.3 or more, and the nonwoven web and the knitted fabric or woven fabric are intertwined with each other. This interlaced non-woven web is processed through the following steps (A) to (D) (A) which is narrower than the thickness of the entangled non-woven web and less than 1/10 of the thickness of the entangled non-woven web. The interlaced nonwoven web is passed through a wide gap in which the upper and lower surfaces of the interwoven nonwoven web are heated to 80°C or higher, and both sides of the interwoven nonwoven web are heated to 80°C or higher. (B) From one side of the smoothed both sides of the interlaced nonwoven web, 10 of the thickness of the smoothed interlaced nonwoven web
Process of penetrating and solidifying the binder to a depth of ~50% (C) Process of filling and fixing an elastic polymer substance into the remaining voids of the entangled nonwoven web where the binder has permeated and solidified (D) The binder dissolves, but After performing the steps of dissolving and removing the binder in the entangled nonwoven web obtained in step (B) in that order using a solvent that does not dissolve the elastic polymer material, the binder is permeated in step (B). A method for producing suede-like artificial leather, characterized by grinding (buffing) the pressed surface. 2. The suede-like artificial leather according to claim 1, wherein one of the nonwoven webs and the other nonwoven web have different single fiber finenesses of the fibers constituting the nonwoven web. Production method. 3. The method for producing suede-like artificial leather according to claim 1 or 2, wherein the average diameter of the single fibers of the thermoplastic synthetic fibers constituting the nonwoven web is 8 μm or less. 4. The method for producing suede-like artificial leather according to claim 1, 2, or 3, wherein the nonwoven web is a nonwoven web obtained by a melt blowing method. 5. The method for producing suede-like artificial leather according to claim 1, 2, 3, or 4, wherein the binder permeates the knitted or woven fabric. 6. Claim 1 or 2, characterized in that the binder does not penetrate into the knitted or woven fabric.
A method for producing suede-like artificial leather according to item 1 or 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1304180A JPS56112576A (en) | 1980-02-07 | 1980-02-07 | Production of suede like artificial leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1304180A JPS56112576A (en) | 1980-02-07 | 1980-02-07 | Production of suede like artificial leather |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56112576A JPS56112576A (en) | 1981-09-04 |
| JPS648753B2 true JPS648753B2 (en) | 1989-02-15 |
Family
ID=11822018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1304180A Granted JPS56112576A (en) | 1980-02-07 | 1980-02-07 | Production of suede like artificial leather |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56112576A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4955673B2 (en) * | 2006-05-30 | 2012-06-20 | 株式会社クラレ | Artificial leather base material and silver-tone artificial leather |
-
1980
- 1980-02-07 JP JP1304180A patent/JPS56112576A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4955673B2 (en) * | 2006-05-30 | 2012-06-20 | 株式会社クラレ | Artificial leather base material and silver-tone artificial leather |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56112576A (en) | 1981-09-04 |
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