JPH0512477B2 - - Google Patents
Info
- Publication number
- JPH0512477B2 JPH0512477B2 JP60072488A JP7248885A JPH0512477B2 JP H0512477 B2 JPH0512477 B2 JP H0512477B2 JP 60072488 A JP60072488 A JP 60072488A JP 7248885 A JP7248885 A JP 7248885A JP H0512477 B2 JPH0512477 B2 JP H0512477B2
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane
- base fabric
- properties
- buffing
- impregnated
- 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
- 239000004814 polyurethane Substances 0.000 claims description 52
- 229920002635 polyurethane Polymers 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 28
- 239000004744 fabric Substances 0.000 claims description 21
- 239000002649 leather substitute Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000004745 nonwoven fabric Substances 0.000 claims description 16
- 230000000704 physical effect Effects 0.000 claims description 13
- 229920001410 Microfiber Polymers 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 11
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 11
- 229920003169 water-soluble polymer Polymers 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000013013 elastic material Substances 0.000 description 6
- -1 polybutylene adipate Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000010985 leather Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 235000015047 pilsener Nutrition 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
発明の分野
本発明はライテイング性（writing effect）に
優れたスエード調人工皮革の製造方法に関する。
さらに詳しくは、本発明は、指でこすつた場合、
その方向へ表面毛羽が向き、周囲と異なる色調を
生ずる、いわゆるライテイング性に優れたスエー
ド調人工皮革の製造方法に関する。
発明の背景
天然スエードは独特な表面特性であるライテイ
ング効果を有するが、このようなライテイング効
果を人工皮革で発現させるには繊度が0.5デニー
ル以下の極細繊維でなければならないことは勿
論、表面毛羽の密度が高く、同時に一定の毛羽長
を有しなければならず、また基布に充填されてい
る高分子弾性体と繊維との間に適当な距離、空隙
が形成されなければならない。
従来のスエード調人工皮革は、不織布に高分子
弾性体を一段で含浸付与してバフイングするため
毛羽の長さが一定せず、また立毛密度が低いため
天然スエードのような優雅な製品を得にくいのが
実情であつた。
特に、スエード製品は、立毛によりその製品評
価が大きく左右され、その用途がしばしば制限さ
れるため、多くの皮革研究者はその解決のため繊
維高分子弾性体表面加工方法など種々の側面から
研究を推進してきた。
例えば米国特許第4206257号などでは、ポリビ
ニルアルコールのような水溶性高分子を不織布に
含浸付与し、高分子弾性体を充填させた後、再び
水溶性高分子を除去することによつて繊維と高分
子弾性体の間に空隙を形成している。
しかし、結局、この空隙は充分ではなかつた
り、あるいは基布の表面部であいかわらず繊維と
高分子弾性体が工程中に結合する可能性が存在す
る。
また、特公昭48−77001号公報などでは皮革状
シート物の表面を塩化亜鉛水溶液などで処理して
高分子弾性体及び繊維を適当に脆化させてバフイ
ング性を向上させる方法を開示しているが、この
ような方法においてもやはり処理液が布の中央部
まで浸透し布の物性を大きく低下させる可能性を
排除することはできない。
また、特公昭55−32828号公報などではバフイ
ングの前に高分子有機シリコン化合物で処理する
方法が記載されているが、このような方法で製造
された製品も触感は良好であるものの立毛が均一
でないなどの問題があつた。
発明の概説
ここに本発明者らは人工皮革に適用される高分
子弾性体の物性及び皮革状シート物内部での充填
状態などを詳細に検討した結果、表面ライテイン
グ（writing）性に非常に優れたスエード調人工
皮革を製造する方法を発明するに至つた。
したがつて、本発明の目的は、一定条件の繊維
を使用して不織布を作り、水溶性高分子を含浸さ
せた後、物性の良好な高分子弾性体とバフイング
性の良好な高分子弾性体とを順に基布の表面部に
充填し、バフイングすることによつてライテイン
グ効果に優れたスエード調人工皮革の製造方法を
提供することにある。
すなわち、本発明は極細繊維化が可能な繊度が
0.001〜0.5デニールの繊維からなる不織布を水溶
性高分子を用いて糊付処理を行なつて基布とし、
該基布に物性の良好なポリウレタン弾性体を第一
次含浸して主に基布の内部に充填を行ない、次い
でバフイング性の良好なポリウレタン弾性体を第
二次含浸して主に基布の表面部に充填し、以後の
表面バフイング性を良好にすることからなる方法
であつて、該繊維がポリエステルまたはポリアミ
ドからなり、該第一次含浸用ポリウレタン弾性体
および第二次含浸用ポリウレタン弾性体がポリエ
ステル−ポリエーテル共重合型であり、該ポリエ
ステル：ポリエーテルの比が重量基準で第一次含
浸用ポリウレタンにおいて20〜50：80〜50、第二
次含浸用ポリウレタンにおいて35〜60：65〜40で
あることを特徴とするライテイング効果に優れた
スエード調人工皮革の製造方法である。
発明の詳説
以下に本発明を詳細に説明する。
本発明は最終製品の繊度が0.001〜0.5デニール
である繊維を使用して高密度不織布を作り、該不
織布に公知のポリビニルアルコールなどの水溶性
高分子を含浸付与した後、引張強伸度などの物性
が良好な高分子弾性体を先ず付与し（第一次含
浸）、次に引張強伸度が低いためバフイング性が
良好な高分子弾性体を特に基布の表面部に充填
（第二次含浸）して、これを染色の前、又は後に
バフイングすることを特徴とするライテイング効
果に優れたスエード調人工皮革を製造する方法で
ある。
ここでバフイング性とはバフイング工程による
立毛発現効果を意味するもので、ライテイング効
果と直結する概念を有する。
５デニール以下の繊維でできたニードルパンチ
ング（needle punching）不織布にポリビニルア
ルコールのような水溶性高分子糊剤を付与する
と、一次的に繊維−繊維間の交錯点に糊剤が付着
してバインダー（binder）効果を現わし、形態安
定性が付与され、且つ、繊維とポリウレタンの間
に空隙が形成され基布が柔軟となり、繊維を極細
化するとき極細繊維束の集束性を高めるなど、多
くの効果が期待される。
第１図に示すごとく、本発明における不織布を
水溶性高分子で糊付した基布の断面は、繊維と繊
維の交絡点ａ及び繊維の表面ｂに一定の厚さで水
溶性高分子が塗布されている。
ついで、このような糊付を行なつた不織布に性
能の異なる２種のポリウレタンを用いて２段階の
浸漬を行なうことによりバフイング性を向上させ
る。これに対して、従来の一般的なポリウレタン
弾性体の製造方法では、ポリエステル、又はポリ
エーテルをソフトセグメントとして、ここに有機
イソシアネートを付加してフリーポリマーとした
後、再びブタンジオールなどの鎖伸張剤を反応さ
せて鎖が非常に長い線状高分子を作る。長年、こ
のようなポリウレタン弾性体が人工皮革製造に用
いられており、現在、かかるポリウレタンの物性
を各用途に適合するよう改良する研究が活発にな
されている。
本発明においてソフトセグメントとして用いら
れる高分子は、ポリエステル系のポリブチレンア
ジペートグリコール、ポリエチレンアジペートグ
リコール、ポリカプロラクトングリコールおよび
エーテル系のポリエチレンエーテルグリコール、
ポリテトラメチレンエーテルグリコールなどが採
用しえ、有機ジイソシアネートとしてはジフエニ
ルメタン−４，4′−ジイソシアネート、ナフタリ
ンジイソシアネート、ジフエニルジイソシアネー
トなどの芳香族ジイソシアネートをはじめ、ヘキ
サメチレンジイソシアネートのような脂肪族ジイ
ソシアネートも使用しうる。鎖伸張剤としてはエ
チレンジアミン、プロピレンジアミン、トリメチ
レンジアミン、テトラメチレンジアミンなどの脂
肪族ジアミンおよびフエニレンジアミン、ナフチ
レンジアミンなどの芳香族ジアミン並びにブタン
ジオール、エチレングリコールなどが使用しうる
が耐熱性、耐高温染色性などの点では芳香族ジア
ミンが好ましい。又、使用される溶剤としてはジ
メチルホルムアミド、ジエチルホルムアミド、ジ
メチルスルホキシド、ジメチルアセトアミドなど
がいずれも用いうるがポリウレタンの溶解性など
により選択しなければならない。
一方、ポリウレタン弾性体はソフトセグメント
の種類及び分子量、ハードセグメント、すなわち
有機イソシアネート、鎖伸張剤の種類及び含有量
などによつてその物理的及び化学的性質が非常に
相違した複雑な構造となしうるが、一般的にエス
テルタイプのポリウレタンは耐加水分解性、耐熱
性などは弱いが高温染色時の柔軟度低下率が優れ
ており、エーテルタイプは柔軟度低下率が小さい
ためゴムのような固い感じであるが耐加水分解
性、耐熱性などは良好である。又、ソフトセグメ
ントの一連の長さ（sequence length）が大きい
ほど引張率や耐熱性などは劣るが、反面伸度は大
きくなるなどその製造工法をはじめ原料高分子の
種類、分子量、含有量、ジイソシアネートと鎖伸
張剤の種類及び含有量などによつて性質が非常に
異なる多くのタイプのポリウレタンとすることが
できる。
従つて、本発明者らはポリウレタンのこのよう
な広範囲な応用可能性に注視し、繊維強度とバフ
イング性の関係を示した第２図のように、繊維の
特性も顧慮し、性質が異なる２種類のポリウレタ
ンを合成した。すなわち、引張強伸度などの物性
が良好なポリウレタン（以下Ａタイプのポリウレ
タン、Ａ−PUと略す）とバフイング性ポリウレ
タン（以下Ｂタイプのポリウレタン、Ｂ−PUと
略す）を合成してこれを糊付不織布に２段階に浸
漬することによつて、基布の内部にはＡ−PUを
充填させ、一方表面部にはＢ−PUを充填させて、
シート物の物性にはＡ−PUが大きく寄与し、Ｂ
−PUは表面のバフイング性を良好にするように
考慮した。
これにより皮革の物性を損なわず優れたバフイ
ング性を有するスエード調人工皮革を得ることが
できる。すなわち、第３図においてｅからｆの範
囲にＡ−PUとＢ−PUの充填量比を調節すると、
以後のバフイング工程において優れたライテイン
グ効果が発揮される。
従来、一種類のポリウレタンで１段の浸漬を行
なう場合は凝固槽投入前のマングル（mangle）
のロール間隔を通常、基布の厚さの80％内外にす
る。もしそれ以上にすると基布の表面部にポリウ
レタンが存在してバフイング性が悪くなり、それ
以下にするとポリウレタン充填量が少なくなりス
エード特有の触感と弾性がなくなり、引張強度も
低下するなどの問題が生じる。
しかし、本発明ではＡ−PU充填時のマングル
ロール間隔を基布の厚さの60％程度とし、再度Ｂ
−PUを浸漬し、パデイング（padding）してＢ
−PUを表面部にのみ充填させるので全体のポリ
ウレタン充填量はロール間隔を80％内外とした場
合とほぼ同一の値を有する。従つて、表面に存在
するＢ−PUによりバフイング性が向上する。
ここで各々のポリウレタンの湿式フイルムの物
性を見ると、次のようである。Ａ−PUは引張強
度50〜80Kg／cm2、100％モデユラス５〜10Kg、300
％モデユラス10〜20Kg／cm2、伸度400〜800％であ
り、Ｂ−PUは引張強度30〜60Kg／cm2、100％モデ
ユラス３〜９Kg／cm2、300％モデユラス５〜15
Kg／cm2、伸度400〜800％である。
本発明において不織布を形成する繊維としては
５デニール以下の繊度を有するものであればよい
が、最終製品においては0.5デニール以下になら
なければ良好なライテイング効果、触感、ウエツ
トタツチ（wet−touch）感などを発揮すること
ができない。
このような極細繊維は連続高分子フイラメント
集束体の中に繊維高分子物を特殊な形態で同時に
溶融紡糸して化学的、物理的な後加工工程におい
て集束体を除去することにより繊維高分子の繊度
0.5デニール以下の極細繊維となる。使用可能な
繊維の種類としてはポリエステル、ポリアミドな
ど繊維形性能を有する高分子であればいずれでも
よい。
一方、不織布に充填する高分子弾性体は、ポリ
エステル−ポリエーテル共重合型ポリウレタンで
ある。
本発明で使用するポリウレタンのポリエステ
ル：ポリエーテル比は、重量基準でＡ−PUが20
〜50：80〜50であり、Ｂ−PUが35〜60：65〜40
である。
本発明で使用される不織布は、上記繊維をクロ
ス−ラツパー（cross−lapper）、ランダム−ラツ
パー（random−lapper）などを用いてウエツブ
（web）とし、このウエツブをニードルパンチン
グ（neddle punching）して３次元結合させる方
法が良好な立毛性を発揮するため好ましい。ベル
トの重量は用途により異なるが、２等分する場合
は300〜700ｇ／m2が作業性の面で最も好ましく、
外見の密度は0.15ｇ／cm3以上とするのがよい。
本発明において再度のポリウレタン浸漬（２段
浸漬）を行なう方法は次のとおりである。
すなわち、スチールロール（steel roll）とゴ
ムロールにより構成されたバス（bath）を有す
るマングル（mangle）を備えた前槽においてＡ
−PUを浸漬して、ついで同じ型式の次のマング
ルでＢ−PUを連続的に浸漬するか、あるいはＡ
−PUを水槽に通し一時的に凝固させた後、スク
イージイング（squeezing）してついでＢ−PUを
浸漬してもよい。
こうして浸漬されたポリウレタンを水中にて凝
固、水洗した後温度を上げ、前に処理された水溶
性高分子を完全に除去する。ポリビニルアルコー
ル（PVA）を主とした水溶性高分子は大体80℃
以上の熱湯で30分以上処理すると完全に脱糊され
るが、糊剤が完全に除去されない場合には皮革状
シート物が硬くならないことがあるので留意しな
ければならない。また、前記繊維の極細化は、上
記したポリウレタン含浸工程前、または後に該繊
維集束体に対する溶媒中で浸漬及びパデイング
（padding）を繰り返すと容易に達成することが
でき、こうして製造した皮革状シート物をサンド
ペーパーでバフイングする。略150メツシユのサ
ンドペーパーにより、皮革状シート物の特性に従
つて１次バフイングして、染色の後、再びバフイ
ングで表面毛羽を整頓すればライテイング効果に
優れたスエード調人工皮革が得られる。
発明の効果
こうして得られた、本発明のスエード調人工皮
革は第４図及び第５図に見られるように表面の毛
羽長が一定して、表面立毛密度が大きくなり結果
的にライテイング効果が増し、触感が非常に柔ら
かくなり、衣類用をはじめ内装剤、鞄用などその
応用範囲が非常に多様なスエード調人工皮革が得
られる。
実施例
以下、本発明の方法によるスエード調人工皮革
の製造方法を実施例により詳細に説明する。
実施例 １
ポリエチレンテレフタレートを極細繊維を形成
する島成分とし、ポリスチレンを極細繊維集束体
（海成分）とした高分子配列体繊維を製造した。
島成分のセグメント（segment）数は30個／filと
して15個／inのクリンプを与えて51mmのステープ
ルとした。これをカーデイング、クロス−ラツピ
ング、ニードルパンチングして重量500ｇ／m2の
不織布とし、ポリビニルアルコール水溶液により
繊維に対して固型分で15％の糊付をした。ここに
ポリエステル−エーテル共重合ポリウレタンを一
次含浸し、再度湿式フイルムの100％モデユラス
３〜９Kg／cm2、300％モデユラス５〜15Kg／cm2の
ポリウレタンを基布の表面部に二次含浸付与した
後、これを凝固して、水洗し脱糊した。これに前
後して過塩素エチレン中で海成分を除去した。以
後、150メツシユのサンドペーパーで非スライス
イング面（非slicing面）をバフイング加工して
表面ライテイング効果に非常に優れたスエード調
人工皮革を得た。
比較例 １
比較のため二次ポリウレタン含浸をしていない
以外、実施例１と同様にして製造した人工皮革の
物性を第１表に示す。
実施例 ２
ナイロンを極細繊維成分とし、ポリスチレンを
極細繊維集束体成分としてブレンデイング紡糸
し、5d×64mmのステープルフアイバーを製造し
て以下実施例１と同様に処理した。
前記各実施例により得られた人工皮革の物性値
を天然スエードの物性と比較して次の第１表に示
す。
FIELD OF THE INVENTION The present invention relates to a method for producing suede-like artificial leather with excellent writing effect.
More specifically, the present invention provides that when rubbed with fingers,
The present invention relates to a method for producing suede-like artificial leather with excellent writing properties, in which the surface fuzz is oriented in that direction and a color tone different from that of the surrounding area is produced. Background of the Invention Natural suede has a unique surface characteristic of a writing effect, but in order to produce such a writing effect in artificial leather, it is necessary to use ultra-fine fibers with a fineness of 0.5 denier or less, as well as surface fluff. It must have a high density and at the same time a certain fluff length, and an appropriate distance and voids must be formed between the fibers and the polymeric elastic material filled in the base fabric. Conventional suede-like artificial leather is made by impregnating a nonwoven fabric with a polymeric elastic material in one step and then buffing it, so the length of the fluff is not constant, and the density of the fluff is low, making it difficult to obtain an elegant product like natural suede. That was the reality. In particular, for suede products, the product evaluation is greatly affected by the nap, and its uses are often limited, so many leather researchers are conducting research from various aspects, such as surface processing methods for fiber polymer elastic materials, to solve this problem. We have been promoting it. For example, in U.S. Patent No. 4,206,257, a nonwoven fabric is impregnated with a water-soluble polymer such as polyvinyl alcohol, filled with a polymer elastic material, and then the water-soluble polymer is removed again. A void is formed between the molecular elastic bodies. However, in the end, there is a possibility that the voids are not sufficient or that the fibers and the polymeric elastomer continue to bond on the surface of the base fabric during the process. In addition, Japanese Patent Publication No. 77001/1984 discloses a method for improving buffing properties by treating the surface of a leather-like sheet with an aqueous solution of zinc chloride to appropriately embrittle the elastic polymer and fibers. However, even with such a method, it is still not possible to exclude the possibility that the treatment liquid will penetrate into the center of the cloth and significantly deteriorate the physical properties of the cloth. In addition, Japanese Patent Publication No. 55-32828 describes a method of treating with a high-molecular organosilicon compound before buffing, but products manufactured by this method also have a good texture, but the raised hair is uniform. There were problems such as not being able to do so. Outline of the invention As a result of detailed study of the physical properties of the polymer elastic material applied to artificial leather and the filling state inside the leather-like sheet material, the present inventors have found that it has extremely excellent surface writing properties. This led to the invention of a method for manufacturing suede-like artificial leather. Therefore, the object of the present invention is to make a nonwoven fabric using fibers under certain conditions, impregnate it with a water-soluble polymer, and then produce an elastomer with good physical properties and an elastomer with good buffing properties. An object of the present invention is to provide a method for producing suede-like artificial leather having an excellent writing effect by sequentially filling the surface of a base fabric with the following materials and buffing the materials. In other words, the present invention has a fineness that allows ultra-fine fiber production.
A nonwoven fabric made of fibers of 0.001 to 0.5 denier is pasted with a water-soluble polymer and used as a base fabric.
The base fabric is first impregnated with a polyurethane elastomer having good physical properties to mainly fill the inside of the base fabric, and then a polyurethane elastomer with good buffing properties is secondly impregnated to mainly fill the inside of the base fabric. A method comprising filling the surface portion to improve subsequent surface buffing properties, the fibers being made of polyester or polyamide, the polyurethane elastomer for primary impregnation and the polyurethane elastomer for secondary impregnation. is a polyester-polyether copolymer type, and the ratio of polyester to polyether is 20 to 50:80 to 50 in the polyurethane for primary impregnation and 35 to 60:65 in the polyurethane for secondary impregnation on a weight basis. This is a method for producing suede-like artificial leather with an excellent writing effect characterized by a hardness of 40%. Detailed Description of the Invention The present invention will be described in detail below. The present invention produces a high-density nonwoven fabric using fibers with a final product fineness of 0.001 to 0.5 denier, and after impregnating the nonwoven fabric with a known water-soluble polymer such as polyvinyl alcohol, First, an elastic polymer with good physical properties is applied (first impregnation), and then an elastic polymer with low tensile strength and elongation and good buffing properties is filled especially on the surface of the base fabric (second impregnation). This is a method for producing suede-like artificial leather with an excellent lighting effect, which is characterized by impregnating the leather and buffing it before or after dyeing. Here, the term "buffing property" refers to the effect of producing pils due to the buffing process, and has a concept that is directly linked to the lighting effect. When a water-soluble polymer sizing agent such as polyvinyl alcohol is applied to a needle-punched nonwoven fabric made of fibers of 5 deniers or less, the sizing agent primarily adheres to the intersections between fibers and binds the binder ( binder) effect, imparts shape stability, creates voids between the fibers and polyurethane, makes the base fabric flexible, and improves the cohesiveness of ultrafine fiber bundles when making the fibers ultrafine. Expected to be effective. As shown in Figure 1, the cross section of the base fabric in which the nonwoven fabric of the present invention is glued with a water-soluble polymer shows that the water-soluble polymer is coated with a constant thickness at the fiber-to-fiber intertwining point a and on the surface b of the fibers. has been done. Next, the nonwoven fabric that has been pasted in this manner is subjected to two-step dipping using two types of polyurethanes having different properties, thereby improving the buffing properties. On the other hand, in the conventional general manufacturing method of polyurethane elastomer, polyester or polyether is used as a soft segment, an organic isocyanate is added thereto to make a free polymer, and then a chain extender such as butanediol is added to the soft segment. react to create linear polymers with very long chains. Such polyurethane elastomers have been used for many years in the production of artificial leather, and active research is currently being carried out to improve the physical properties of such polyurethanes to suit various uses. The polymers used as the soft segment in the present invention include polyester-based polybutylene adipate glycol, polyethylene adipate glycol, polycaprolactone glycol, and ether-based polyethylene ether glycol.
Polytetramethylene ether glycol etc. can be used, and as the organic diisocyanate, aromatic diisocyanates such as diphenylmethane-4,4'-diisocyanate, naphthalene diisocyanate, diphenyl diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate can also be used. sell. As chain extenders, aliphatic diamines such as ethylene diamine, propylene diamine, trimethylene diamine, and tetramethylene diamine; aromatic diamines such as phenylene diamine and naphthylene diamine; butane diol and ethylene glycol; Aromatic diamines are preferred in terms of high-temperature dyeing resistance. The solvent to be used may be dimethylformamide, diethylformamide, dimethylsulfoxide, dimethylacetamide, etc., but the solvent must be selected depending on the solubility of the polyurethane. On the other hand, polyurethane elastomers can have complex structures with very different physical and chemical properties depending on the type and molecular weight of the soft segment, the type and content of the hard segment, that is, the organic isocyanate, and the chain extender. However, in general, ester type polyurethane has poor hydrolysis resistance and heat resistance, but has an excellent flexibility reduction rate during high-temperature dyeing, while ether type polyurethane has a low flexibility loss rate, giving it a hard, rubber-like feel. However, it has good hydrolysis resistance and heat resistance. In addition, the larger the sequence length of the soft segment, the worse the tensile modulus and heat resistance, but on the other hand, the higher the elongation. There can be many types of polyurethane, which have very different properties depending on the type and content of the chain extender. Therefore, the present inventors paid close attention to such a wide range of applicability of polyurethane, and considered the characteristics of the fiber, as shown in Figure 2, which shows the relationship between fiber strength and buffing property, and developed two materials with different properties. Various types of polyurethane were synthesized. That is, polyurethane with good physical properties such as tensile strength and elongation (hereinafter referred to as A-type polyurethane, A-PU) and buffing polyurethane (hereinafter referred to as B-type polyurethane, referred to as B-PU) are synthesized, and this is made into a paste. By dipping the nonwoven fabric in two stages, the inside of the base fabric is filled with A-PU, while the surface area is filled with B-PU.
A-PU greatly contributes to the physical properties of sheet materials, and B
-PU was considered to improve surface buffing properties. This makes it possible to obtain suede-like artificial leather that has excellent buffing properties without impairing the physical properties of the leather. That is, when the filling ratio of A-PU and B-PU is adjusted to the range from e to f in Fig. 3,
Excellent lighting effects are exhibited in the subsequent buffing process. Conventionally, when performing one-stage immersion with one type of polyurethane, a mangle was used before entering the coagulation tank.
The roll spacing is usually within 80% of the base fabric thickness. If the amount is more than this, polyurethane will be present on the surface of the base fabric, which will deteriorate the buffing properties, and if it is less than that, the amount of polyurethane filled will decrease, and the feel and elasticity unique to suede will be lost, and there will be problems such as a decrease in tensile strength. arise. However, in the present invention, the mangle roll interval when filling A-PU is set to about 60% of the thickness of the base fabric, and B
- Dip PU and padding B
- Since PU is filled only in the surface area, the total polyurethane filling amount is approximately the same as when the roll spacing is set to around 80%. Therefore, the B-PU present on the surface improves buffing properties. Here, the physical properties of each polyurethane wet film are as follows. A-PU has tensile strength of 50-80Kg/ cm2 , 100% modulus of 5-10Kg, 300
% modulus 10-20 Kg/cm 2 , elongation 400-800%, B-PU has tensile strength 30-60 Kg/cm 2 , 100% modulus 3-9 Kg/cm 2 , 300% modulus 5-15
Kg/cm 2 and elongation of 400 to 800%. In the present invention, the fibers forming the nonwoven fabric may have a fineness of 5 denier or less, but in the final product, if the fineness is 0.5 denier or less, good writing effect, tactile feel, wet-touch feeling, etc. unable to demonstrate. Such ultrafine fibers are produced by simultaneously melt-spinning fiber polymers in a special form into continuous polymer filament bundles and removing the bundles in chemical and physical post-processing steps. fineness
Ultra-fine fibers of 0.5 denier or less. As the type of fiber that can be used, any polymer having fiber-forming properties such as polyester and polyamide may be used. On the other hand, the polymeric elastic material filled in the nonwoven fabric is a polyester-polyether copolymer type polyurethane. The polyester:polyether ratio of the polyurethane used in the present invention is 20% by weight of A-PU.
~50:80~50 and B-PU is 35~60:65~40
It is. The nonwoven fabric used in the present invention is produced by forming the above-mentioned fibers into a web using a cross-lapper, a random-lapper, etc., and then needle punching this web. A method of three-dimensional bonding is preferable because it exhibits good napping properties. The weight of the belt varies depending on the application, but when dividing it into two equal parts, 300 to 700 g/ m2 is most preferable in terms of workability.
The external density is preferably 0.15 g/cm 3 or more. In the present invention, the method for performing polyurethane dipping again (two-step dipping) is as follows. That is, A in a front tank equipped with a mangle having a bath composed of a steel roll and a rubber roll.
- immerse PU and then successively immerse B-PU in the next mangle of the same type or A
- The PU may be passed through a water bath to temporarily solidify, followed by squeezing and then immersion of the B-PU. The polyurethane soaked in this way is coagulated in water, washed with water, and then the temperature is raised to completely remove the previously treated water-soluble polymer. Water-soluble polymers, mainly polyvinyl alcohol (PVA), are heated to about 80℃.
If treated with the above boiling water for 30 minutes or more, the size will be completely removed, but care must be taken as the leather-like sheet may not become hard if the size is not completely removed. Further, the ultra-fine fibers can be easily achieved by repeating dipping and padding of the fiber bundle in a solvent before or after the polyurethane impregnation step, and the leather-like sheet produced in this way can be easily achieved. Buff with sandpaper. A suede-like artificial leather with an excellent writing effect can be obtained by first buffing with approximately 150 mesh sandpaper according to the characteristics of the leather-like sheet material, and after dyeing, buffing is performed again to tidy up the surface fuzz. Effects of the Invention As shown in FIGS. 4 and 5, the suede-like artificial leather of the present invention thus obtained has a constant surface nap length, a high surface nap density, and a resulting increased lighting effect. This produces suede-like artificial leather that is extremely soft to the touch and has a wide range of applications, including clothing, interior decoration materials, and bags. Examples Hereinafter, the method for producing suede-like artificial leather according to the method of the present invention will be explained in detail with reference to Examples. Example 1 A polymer array fiber was produced using polyethylene terephthalate as an island component forming ultrafine fibers and polystyrene as an ultrafine fiber bundle (sea component).
The number of segments of the island component was 30/fil, and 15/in crimps were applied to make a 51 mm staple. This was carded, cross-wrapped and needle-punched to form a non-woven fabric with a weight of 500 g/m 2 , and the fibers were pasted with a solid content of 15% using an aqueous polyvinyl alcohol solution. This was firstly impregnated with polyester-ether copolymerized polyurethane, and the surface of the base fabric was secondarily impregnated with polyurethane of a wet film with a 100% modulus of 3 to 9 kg/cm 2 and a 300% modulus of 5 to 15 kg/cm 2 . Thereafter, this was coagulated, washed with water, and desized. Before and after this, the sea component was removed in perchlorethylene. Thereafter, the non-slicing surface was buffed using 150 mesh sandpaper to obtain suede-like artificial leather with an excellent surface writing effect. Comparative Example 1 For comparison, Table 1 shows the physical properties of artificial leather produced in the same manner as in Example 1, except that it was not impregnated with secondary polyurethane. Example 2 Nylon was used as an ultrafine fiber component and polystyrene was used as an ultrafine fiber bundle component by blending and spinning to produce a staple fiber of 5 d x 64 mm, which was then treated in the same manner as in Example 1. The physical properties of the artificial leather obtained in each of the Examples above are compared with those of natural suede and are shown in Table 1 below.
【表】
前記の通り本発明の方法によつて製造されたス
エード調人工皮革は第１表から明らかなごとく、
剛軟度、ライテイング効果において著しい向上が
見られる。[Table] As is clear from Table 1, the suede-like artificial leather produced by the method of the present invention as described above is as follows:
Significant improvements can be seen in bending resistance and lighting effect.
第１図は不織布を糊付した状態の模式図、第２
図は繊維強度とバフイング性（buffing）との関
係を示すグラフ、第３図は２種のポリウレタン組
成比に対するバフイング性及び皮革引張強度の関
係を示すグラフ、第４図は本発明の方法によつて
製造された人工皮革表面の繊維の形状を示す電子
顕微鏡による図面代用写真、第５図は本発明の方
法によつて製造された人工皮革側面の繊維の形状
を示す電子顕微鏡による図面代用写真である。
Figure 1 is a schematic diagram of the state in which the nonwoven fabric is glued, Figure 2
Figure 3 is a graph showing the relationship between fiber strength and buffing property, Figure 3 is a graph showing the relationship between buffing property and leather tensile strength for two types of polyurethane composition ratios, and Figure 4 is a graph showing the relationship between the buffing property and leather tensile strength according to the method of the present invention. Figure 5 is a photograph taken in place of a drawing taken by an electron microscope showing the shape of fibers on the surface of the artificial leather manufactured by the method of the present invention. be.
Claims (1)
の繊維からなる不織布を水溶性高分子を用いて糊
付処理を行なつて基布とし、該基布に物性の良好
なポリウレタン弾性体を第一次含浸して主に基布
内部の充填を行ない、次いでバフイング性の良好
なポリウレタン弾性体を第二次含浸して主に基布
の表面部に充填し、以後の表面バフイング性を良
好にすることからなる方法であつて、該繊維がポ
リエステルまたはポリアミドからなり、該第一次
含浸用ポリウレタン弾性体および第二次含浸用ポ
リウレタン弾性体がポリエステル−ポリエーテル
共重合型であり、該ポリエステル：ポリエーテル
の比が重量基準で第一次含浸用ポリウレタンにお
いて20〜50：80〜50、第二次含浸用ポリウレタン
において35〜60：65〜40であることを特徴とする
ライテイング効果に優れたスエード調人工皮革を
製造する方法。 ２ バフイング性の良好なポリウレタンが湿式フ
イルム成形時、密度0.2〜0.5ｇ／cm3、100％モデ
ユラス３〜９Kg／cm2、300％モデユラス５〜15
Kg／cm2である特許請求の範囲第１項記載の方法。 ３ 第二次含浸ポリウレタンの付与量が第一次含
浸量の10〜50重量％である特許請求の範囲第１項
記載の方法。[Scope of Claims] 1 A nonwoven fabric made of fibers with a fineness of 0.001 to 0.5 denier that can be made into ultra-fine fibers is treated with a water-soluble polymer to form a base fabric, and the base fabric has good physical properties. The polyurethane elastomer is first impregnated to mainly fill the inside of the base fabric, and then the polyurethane elastomer with good buffing properties is secondly impregnated to mainly fill the surface of the base fabric, and the subsequent surface is filled. A method comprising improving buffing properties, wherein the fiber is made of polyester or polyamide, and the polyurethane elastomer for primary impregnation and the polyurethane elastomer for secondary impregnation are of a polyester-polyether copolymer type. Lighting characterized in that the polyester:polyether ratio is 20-50:80-50 in the polyurethane for primary impregnation and 35-60:65-40 in the polyurethane for secondary impregnation on a weight basis. A method for producing highly effective suede-like artificial leather. 2. Polyurethane with good buffing properties has a density of 0.2 to 0.5 g/cm 3 , a 100% modulus of 3 to 9 Kg/cm 2 , and a 300% modulus of 5 to 15 during wet film molding.
The method according to claim 1, wherein the amount is Kg/cm 2 . 3. The method according to claim 1, wherein the amount of the second impregnated polyurethane is 10 to 50% by weight of the first impregnated amount.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1984P2818 | 1984-05-23 | ||
| KR1019840002818A KR860001654B1 (en) | 1984-05-23 | 1984-05-23 | A method for preparation of sweater artificial fiber with excellent writing effect |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS616379A JPS616379A (en) | 1986-01-13 |
| JPH0512477B2 true JPH0512477B2 (en) | 1993-02-18 |
Family
ID=19233942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60072488A Granted JPS616379A (en) | 1984-05-23 | 1985-04-04 | Production of suede like artificial leather excellent in writing effect |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS616379A (en) |
| KR (1) | KR860001654B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105452559B (en) * | 2013-09-13 | 2017-11-21 | 东丽株式会社 | Tablet and its manufacture method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832302A (en) * | 1971-08-31 | 1973-04-28 | ||
| JPS55506A (en) * | 1978-05-26 | 1980-01-05 | Olympus Optical Co Ltd | Control method of stencil master plate making device by electrophotographic method |
-
1984
- 1984-05-23 KR KR1019840002818A patent/KR860001654B1/en not_active IP Right Cessation
-
1985
- 1985-04-04 JP JP60072488A patent/JPS616379A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832302A (en) * | 1971-08-31 | 1973-04-28 | ||
| JPS55506A (en) * | 1978-05-26 | 1980-01-05 | Olympus Optical Co Ltd | Control method of stencil master plate making device by electrophotographic method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS616379A (en) | 1986-01-13 |
| KR850008373A (en) | 1985-12-16 |
| KR860001654B1 (en) | 1986-10-15 |
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