JP2004339614A - Method for producing grained artificial leather - Google Patents
Method for producing grained artificial leather Download PDFInfo
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- JP2004339614A JP2004339614A JP2003134186A JP2003134186A JP2004339614A JP 2004339614 A JP2004339614 A JP 2004339614A JP 2003134186 A JP2003134186 A JP 2003134186A JP 2003134186 A JP2003134186 A JP 2003134186A JP 2004339614 A JP2004339614 A JP 2004339614A
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- artificial leather
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、銀付調人工皮革の製造方法、さらに詳しくは良好なしぼ感と風合いに優れた銀付調人工皮革の製造方法に関する。
【0002】
【従来の技術】
近年、天然皮革代替物として、繊維集合体と高分子弾性体からなる基材表面にコート層を積層した銀付調人工皮革が、軽さ、イージーケアー、低価格などの特徴から、衣料用、一般資材およびスポーツ分野などに幅広く利用されている。
【0003】
そして、基材に含まれる高分子弾性体としては、微多孔が存在するものが風合的に優れたものとなることが知られており、一般には湿式凝固法と呼ばれる方法によって製造されることが多い。しかし湿式凝固させるためには長い時間が必要であり、有機溶剤を用いる点からも必然的に大きく価格の高い専用設備を必要とするという問題があった。
【0004】
そこで、最近では溶剤系の湿式凝固法ではなく、従来充実層しか出来なかった水系ポリウレタンの感熱凝固法等を改良し、多孔を有する層を形成させることが試みられている。例えば特許文献1には、水系の感熱凝固性ポリウレタンエマルジョン及び熱膨張性プラスチックマイクロバルーンを含む組成物を40〜190℃の水又は水蒸気中で処理する方法が開示されている。しかしこの方法では含浸層全体に多孔が生成し、かつ発泡によって厚さが処理前の3〜5倍にもなり、折り曲げた際に挫掘による大皺が生じ、風合いが劣るという問題があった。
【0005】
【特許文献1】
特公平6−60260号公報
【0006】
【発明が解決しようとする課題】
本発明は上記従来技術の有する問題点を鑑みなされたもので、その目的は、良好なしぼ感と風合に優れ、靴、衣料用の天然皮革代替物に好適に用いられる銀付調人工皮革の製造方法を提供することにある。
【0007】
【課題を解決するための手段】
本発明の銀付調人工皮革の製造方法は、アミノ変性シリコーンであらかじめ処理されている繊維質基材上に、高分子弾性体エマルジョンと殻壁軟化点温度が80℃以上の熱膨張性カプセルを含む含浸液を表面側から塗布し、殻壁軟化点温度より低い温度で予備乾燥することを複数回繰り返した後に、殻壁軟化点以上の温度で熱膨張性カプセルを発泡させると同時に含浸液を乾燥させ、引き続き表面側に高分子弾性体からなるコート層を付与することを特徴とする。
【0008】
さらには該繊維質基材が、0.5dtex以下の極細繊維からなるものであることや、該熱膨張性カプセルの直径が5〜50μmであることが好ましい。
【0009】
【発明の実施の形態】
以下、本発明について詳細に説明する。
本発明の製造方法では、まず繊維質基材上に高分子弾性体エマルジョンと熱膨張性カプセルとを含む含浸液を表面側から塗布する。
【0010】
繊維質基材を構成する繊維は通常の太さの繊維でもよいが、風合い面から極細繊維であることが好ましい。極細繊維の繊度としては0.5dtex以下であることが好ましく、さらには0.001〜0.3dtexであることが好ましい。また繊維質基材を作成するために用いるこのような繊維としては、最終的に上記のような極細繊維となる繊維であれば好ましく、そのような極細化前の繊維としては海島型の混合紡糸繊維、複合紡糸繊維などいずれもが適用できるが、特に好ましくは剥離分割型複合繊維であることである。
【0011】
本発明で用いられるこのような繊維としては、ポリエステル、ポリアミド、ポリアクリル、ポリオレフィンなどの従来公知の繊維形成可能な合成樹脂の一種、あるいは二種以上の樹脂からなる合成繊維が使用出来る。この中でも、ポリエステル、ポリアミドまたはポリエステル/ポリアミドからなるものを用いることが特に好ましい。繊維となるポリエステルとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリプロピレンテレフタレートなどがあげられ、ポリアミドとしては、ナイロン−6、ナイロン−66、ナイロン−12などがあげられる。中でもポリエチレンテレフタレート、ナイロン−6などが、工程安定性やコスト面から好ましい。
【0012】
また、本発明では、極細化前の繊維でシートを作成し、極細化処理を経て繊維質基材とすることが好ましい。さらにこのときシートを構成する極細化前の繊維には熱収縮性繊維が含まれていることが好ましい。シート形状とした後で熱により繊維を収縮させることにより、高分子弾性体の含浸前に繊維の密度を高くでき、風合いが向上する。このような熱収縮性繊維としては、特に好ましくは収縮応力が大きい高収縮ポリエステル系繊維である。例えばポリエチレンテレフタレートを主成分とする繊維形成性ポリマーを紡糸した後、温水中で低倍率延伸して得られる熱収縮性繊維などである。さらに、該熱収縮性繊維は延伸条件などの制御により50℃以上100℃以下で収縮特性を発現するものが好ましい。50℃より低い温度で特性を発現するものは品質のバラツキの要因になり、100℃より高い温度で特性を発現するものは、多くの熱量を必要し生産性が悪くなる。シートとした後、繊維質基材となるまでの収縮率は5〜50%、特には20〜40%であることが好ましい。
【0013】
また、最も好ましくはシートを構成する繊維が、熱収縮性繊維から構成され、さらに2種以上の単繊維に分割可能な複合繊維であることである。このように該複合繊維を分割して発生するそれぞれの単繊維の熱収縮性が互いに異なる場合は、収縮処理時に複合繊維の分割がさらにすすみ、より緻密でかつ均質な構造を得ることが出来る。例えば、熱収縮性の高いポリエステル系繊維と熱収縮性の低いポリアミド系繊維とに、最終的に分割、極細繊維化される剥離分割型複合繊維などが好ましい。
【0014】
これらの繊維からなるシートとしては風合い面からすると不織布であることがもっとも好ましい。このような不織布を形成する方法は、短繊維からのカーディング、交絡処理による方法、あるいは長繊維のダイレクトシート化、交絡処理による方法などの従来から公知の方法が採用できる。さらに緻密でかつ均質な繊維質基材を得るためには、極細繊維化される剥離分割型複合繊維を用い、高圧水流により絡合させる方法が好ましい。
【0015】
本発明の銀付調人工皮革の製造方法では、該繊維質基材はあらかじめアミノ変性シリコーンで処理しておくことが必要である。一般にはアミノ変性シリコーンを付着させ、乾燥処理する。本発明ではアミノ変性シリコーンが高分子弾性体の含浸前に繊維間に働くことにより、繊維と高分子弾性体との接着が防止され、より柔軟な構造となる。
【0016】
本発明の製造方法における、好ましいアミノ変性シリコーン成分の付着量としては、該繊維質基材重量に対し0.1〜2重量%、さらに好ましくは0.5〜1重量%であることである。処理方法としては、濃度0.1〜1重量%に水で希釈し調製した液を繊維質基材に含浸し、ニップロールで絞り付着量をコントロールし、次いで乾燥させることによって得ることができる。乾燥方法は熱風乾燥でも良いが、加熱ロールに接触させて乾燥させることにより表面の平滑性も同時に得ることができる。また本発明では樹脂の含浸前に処理するために、このような少ない付着量であるにも係わらず高い効果が得られ、かつ最終的に得られる皮革様シート状物からの脱落が非常に少ない。
【0017】
本発明の製造方法では、このように処理された繊維質基材に高分子弾性体エマルジョンと、殻壁軟化点温度が80℃以上の熱膨張性カプセルとを含む含浸液を表面側から塗布する。
本発明に用いる高分子弾性体エマルジョンとしては、水の除去後にエラストマー性を示すものであればいずれでも良いが、中でもポリウレタンエマルジョンが柔軟性、強度、耐候性などの点から好ましい。
【0018】
さらに本発明においては、該高分子弾性体エマルジョンが感熱凝固特性を有していることが好ましい。高分子弾性体エマルジョンの凝固特性が発現する温度は熱膨張性カプセルの膨張開始温度以下で凝固特性を発現するものが好ましい。高分子弾性体エマルジョンの凝固特性が発現する温度とは、種々の添加剤を配合したエマルジョンを攪拌しながら昇温した時に、エマルジョンが流動性を失い凝固する温度である。
【0019】
本発明で用いる熱膨張性カプセルとしては、熱可塑性樹脂を殻とし、膨張剤として、特定の沸点を有する有機化合物を内包、カプセル化したものが挙げられる。例えば塩化ビニリデン・アクリロニトリルコポリマーを殻として、イソブタンを内包、カプセル化したもの等が挙げられる。その直径としては5〜50μmであることが好ましい。本発明の熱膨張性カプセルは加熱により殻が軟化し、内包された有機化合物が気体となって膨張するものである。熱可塑性樹脂の種類、殻の厚み、カプセルの直径等により、膨張開始温度及び最高膨張点を変化させることができる。
また、処理する含浸液としては、高分子弾性体の固型分重量に対する熱膨張性カプセルの固型分重量が2〜10重量%であることが好ましい。
【0020】
さらに上記エマルジョンの耐光性、耐熱性、耐水性、耐溶剤性等の各種耐久性を改善する目的で酸化防止剤、紫外線吸収剤、加水分解防止剤等の安定剤や、エポキシ樹脂、メラミン樹脂、イソシアネート化合物、アジリジン化合物、ポリカルボジイミド化合物等の架橋剤を配合して使用することもできる。さらに、着色を目的として水溶性あるいは水分散性の各種無機、有機顔料を配合することができる。
【0021】
本発明の含浸液を繊維質基材に含浸する方法は、表面側から塗布する方法であり、グラビアコーティング法が好ましく用いられる。塗布回数としては2回以上であれば良いが、工業的に考えるとせいぜい10回以内であれば十分であり、一般的には5回以内である。1回の塗布による付着量(固形分)は、乾燥後の重量で繊維重量の5〜15重量%であり、かつ総塗布量が50重量%以下であることが好ましい。このように複数回塗布する場合には1回あたりの付着量を15重量%以下とするとともに、回数を重ねる毎に付着量を少なくすることが好ましい。このように何回かに分けて塗布することにより、表面側に高分子弾性体と繊維とからなる含浸層が形成され、熱膨張性カプセルはその最表面側に偏在させることができる。最初の塗布により繊維質基材の表面の空隙が少なくなり、再度の塗布では高分子弾性体だけが内部に侵入し、直径の比較的大きい熱膨張性カプセルは表面に残るためである。
【0022】
さらに安定に塗布するためには、塗布の途中に追加の予備乾燥を行い、不要な水分を揮発させることが好ましい。例えば、複数回、塗布、予備乾燥を繰り返した後、さらに追加の予備乾燥を行い、その後さらに複数回、塗布、予備乾燥を繰り返すことで、予備乾燥の時間を5〜60秒程度の短時間に抑えることができる。このとき追加の予備乾燥は2〜30分程度の長時間とすることが好ましい。
【0023】
含浸段階での高分子弾性体の付着量は、好ましくは、繊維質基材100重量部に対し3〜50重量%である。高分子弾性体付着量(固形分)が少ないと得られるシートの充実感が低下し、逆に多いと硬くなる傾向がある。
【0024】
本発明では含浸液を表面から塗布し、殻壁軟化点温度より低い温度で予備乾燥する塗布予備乾燥工程後に、さらに含浸液を表面から塗布することが必要である。塗布量を安定化するためには、先に述べたように2〜3回に分けて少量ずつ塗布することが好ましい。
【0025】
使用している高分子弾性体が感熱凝固性を有する場合には、この予備乾燥の温度は感熱凝固温度以上であることが好ましい。このような予備乾燥を行うことによりマイグレーションによる高分子弾性体の過度の浸透を防止することができ、さらに複数回に分けて塗布しているために発泡体は表面に多く偏在し、内部にはほとんど存在しない。
このように再度含浸液を塗布した後に、殻壁軟化点以上の温度で熱膨張性カプセルを発泡させると同時に含浸液を乾燥させる。
【0026】
本発明ではさらにその高分子弾性体を塗布し乾燥した表面側に、高分子弾性体からなるコート層を付与することが必要である。このときに用いる高分子弾性体としては特に制限はないが、風合い面等からポリウレタン樹脂であることが最も好ましい。
【0027】
また、この際少量なら熱膨張性カプセルを含んでも良いが、平滑性を出すためには含まないことが好ましい。また、コート方法としては従来公知の方法を用いることができるが、表面の平滑性や柄模様を満足しやすいラミネート法であることが好ましい。例えば離型紙上に高分子弾性体のフィルム層を形成し、高分子弾性体のバインダー層を塗布して含浸基材に張り合わせる方法である。水系のラミネート法を用いる場合には、熱シリンダーでニップすることが好ましい。
【0028】
このようにして本発明の製造方法で得られた銀付調人工皮革は、高分子弾性体に空隙が存在し、かつ基材の内部に少なく、コート層のすぐ下の部分に多いため適切な風合いとなり、良好なしぼ感と風合に優れ、靴、衣料用の天然皮革代替物に好適に用いられる銀付調人工皮革となる。
【0029】
【実施例】
以下に実施例をあげて本発明をさらに具体的に説明するが、本発明はこれら実施例により限定されるものではない。なお、実施例および比較例における部および%は、特に断らない限り重量基準である。
【0030】
実施例中の、「しぼ感」、「風合い」に関しては、良い順に○、△、×で判定し、「うき皺」は折り曲げた際のうき皺の発生の有無で判断し、うき皺の発生の無いものを○、小さな皺が発生するものを△、大きな皺が発生するものを×とした。また、「含浸ポリウレタン塗布量」は、各グラビアロール塗布毎に、「浸透度」は目視で断面を確認し表面からの高分子弾性体の浸透距離を断面の全体厚さで除した数値(%)を、「R/F」は未含浸部分、含浸部分を分けずに繊維複合シート全体の高分子弾性体/繊維の比率(%)を求めた。
【0031】
[実施例1]
(繊維質基材の作成)
第1成分として収縮特性を有するポリエチレンテレフタレート、第2成分をナイロン−6とする16分割歯車型の断面を有する親糸繊度4.4dtexの剥離分割型複合繊維を、ニードルパンチと高圧水流交絡処理により、繊維の絡合と分割処理を行い、厚さ1.05mm、目付け241g/m2の不織布とし、次いでこの分割処理後の不織布を75℃の温水槽中に20秒間浸漬し、第1成分のポリエチレンテレフタレート繊維を収縮させ、全体の面積を21%収縮させ繊維質基材となる不織布を得た。
【0032】
(シリコーン処理)
参考例1で得られた不織布に、ポロン MF−14(アミノ変性シリコーン柔軟剤、信越化学工業(株)製、固形分濃度15重量%)/水=2/98(重量部)をウェットピックアップ、200重量%で柔軟処理、120℃で5分間乾燥させ不織布を得た。
【0033】
(含浸液の作成)
V−2114(水性ポリウレタン樹脂、大日本インキ化学工業(株)製、固形分濃度40重量%)/DISPERSE HG−950(水分散性黒顔料、大日本インキ化学工業(株)製)/ハイドラン WLアシスターT2(ウレタン系増粘剤、大日本インキ化学工業(株)製)/F−90N(溌水剤、明成化学工業(株)製)/SD−8i(疎水剤、大日本インキ化学工業(株)製)/マツモトマイクロスフェア−F−50(低沸点炭化水素含有の熱膨張性マイクロカプセル、松本油脂製薬(株)製)/水=70/1/1/1/1/26(重量部)で配合し、グラビア塗布するための含浸液(720mPa・s、20℃)を作成した。
【0034】
(繊維複合シートの作成)
シリコーン処理をした上記収縮不織布に、グラビアロール(#110)で塗布し、予備乾燥(110℃、20秒)する工程を4ロール分繰り返した。また2ロール分塗布後の中間工程には90℃、10分の予備乾燥を追加した。全4ロール塗布、予備乾燥後に130℃、5分で発泡、乾燥させ、繊維複合シートを得た。
【0035】
電子顕微鏡で断面、表面状態を観察すると発泡剤は表層部にのみ存在し、大きさは100μm以下で、表面は発泡剤と繊維が観察された。
【0036】
(コート層の作成)
ハイドラン WLS211(水性ポリウレタン樹脂、大日本インキ化学工業(株)製、固型分濃度35重量%)/DISPERSE HG(水分散性黒顔料、大日本インキ化学工業(株)製)/ハイドラン WLアシスターT1(ウレタン系増粘剤、大日本インキ化学工業(株)製)/ハイドラン WLアシスターC2(イソシアネート系架橋剤、大日本インキ化学工業(株)製)/ハイドラン WLアシスターW1(レベリング剤、大日本インキ化学工業(株)製)/ハイドラン アシスターD1(消泡剤、大日本インキ化学工業(株)製)=100/5/0.25/4/0.2/5(重量部)で配合したフィルム層用配合液を離型紙(AR―144SM、厚さ0.25mm、旭ロール(株)製)上に塗布厚100μm(wet)で塗布し、初めに70℃で2分間、次いで110℃で4分間の2段階で乾燥を行い、ポリウレタン樹脂フィルム(以下フィルム層という)を形成した。
【0037】
その表面にさらに、ハイドラン WLA311(水性ポリウレタン樹脂、大日本インキ化学工業(株)製、固型分濃度45重量%)/DISPERSE HG(水分散性黒顔料、大日本インキ化学工業(株)製)/ハイドラン WLアシスターT1(ウレタン系増粘剤、大日本インキ化学工業(株)製)/ハイドラン WLアシスターC2(イソシアネート系架橋剤、大日本インキ化学工業(株)製)=100/5/0.1/10(部)で配合した接着剤配合液を塗布厚150μm(wet)で塗布し、ラミネート層を作成した。離型紙上の塗布液の含水率を測定したところ、45.8%であった。
【0038】
(銀付調人工皮革1の作成)
上記のコート層を、直ちに繊維複合シート1に貼り合せ、熱シリンダー(表面温度130℃)に接触させて15秒間前加熱をかけ、その後クリアランス1.0mmの条件下で該熱シリンダーを用いて熱ニップし、さらに120℃で2分間のキュアリングを行った。キュアリング後の基材の含水率は4.1%であった。さらに、50℃で24時間エージングを行い、離型紙を剥ぎ取り銀付調人工皮革1を得た。
物性等を表1に示す。
【0039】
[実施例2]
実施例1のシリコーン処理を、ポロン MF−14(アミノ変性シリコーン柔軟剤、信越化学工業(株)製)/水=3/97(重量部)に変更した以外は、実施例1と同様に銀付調人工皮革を作成した。
【0040】
電子顕微鏡でコート層付与前の繊維複合シートの断面、表面状態を観察すると発泡剤は表層部にのみ存在し、大きさは100μm以下で、表面は発泡剤と繊維が観察された。
物性等を表1に併せて示す。
【0041】
[実施例3]
実施例1のシリコーン処理を、ポロン MF−14(アミノ変性シリコーン柔軟剤、信越化学工業(株)製)/水=4/96(重量部)に変更した以外は、実施例1と同様に銀付調人工皮革を作成した。
【0042】
電子顕微鏡でコート層付与前の繊維複合シートの断面、表面状態を観察すると発泡剤は表層部にのみ存在し、大きさは100μm以下で、表面は発泡剤と繊維が観察された。
物性等を表1に併せて示す。
【0043】
[比較例1]
実施例1のシリコーン処理を行わなかった以外は、実施例1と同様に銀付調人工皮革を作成した。
【0044】
電子顕微鏡でコート層付与前の繊維複合シートの断面、表面状態を観察すると発泡剤は表層部にのみ存在し、大きさは100μm以下で、表面は発泡剤と繊維が観察されてはいるものの、風合いの劣ったものだった。
物性等を表1に併せて示す。
【0045】
[比較例2]
実施例1の予備乾燥を行わない以外は、実施例1と同様に銀付調人工皮革を作成した。
【0046】
含浸ポリウレタンが内部まで浸透し、さらに乾燥時にダンボール構造となり風合いの劣ったものだった。物性等を表1に併せて示す。
【0047】
[比較例3]
実施例1のグラビア塗布の代わりに、含浸液に繊維質基材を浸漬し、ニップすることによりR/Fが35%の繊維複合シートを作成し、その後は実施例1と同様にコート層を付与した。
【0048】
含浸ポリウレタン及び発泡剤が内部まで浸透し、風合いの劣ったものだった。物性等を表1に併せて示す。
【0049】
【表1】
【0050】
【発明の効果】
本発明の製造方法は、良好なしぼ感と風合に優れ、靴、衣料用の天然皮革代替物に好適に用いられる銀付調人工皮革の製造方法である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing artificial leather with silver tone, and more particularly, to a method for producing artificial leather with silver grain having excellent graininess and texture.
[0002]
[Prior art]
In recent years, as an alternative to natural leather, artificial leather with silver on which a coat layer is laminated on the surface of a base material composed of a fiber aggregate and a polymer elastic body has been used for clothing, because of its features such as lightness, easy care, and low price. Widely used in general materials and sports fields.
[0003]
It is known that, as the polymer elastic body contained in the base material, those having microporosity are excellent in feeling, and are generally manufactured by a method called wet coagulation method. There are many. However, a long time is required for wet coagulation, and there is a problem that a dedicated equipment that is inevitably large and expensive is required in terms of using an organic solvent.
[0004]
Therefore, recently, instead of the solvent-based wet coagulation method, an attempt has been made to improve the heat-sensitive coagulation method or the like of water-based polyurethane, which conventionally could only form a solid layer, to form a porous layer. For example, Patent Literature 1 discloses a method of treating a composition containing an aqueous thermosetting polyurethane emulsion and thermally expandable plastic microballoons in water or steam at 40 to 190 ° C. However, in this method, there is a problem in that porosity is generated in the entire impregnated layer, and the thickness becomes 3 to 5 times as large as that before treatment due to foaming, and when folded, large wrinkles due to burring occur, resulting in poor texture. .
[0005]
[Patent Document 1]
Japanese Patent Publication No. 6-60260
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object an artificial leather with silver tone which is preferably used as a natural leather substitute for shoes and clothing, having an excellent graininess and feeling. It is to provide a manufacturing method of.
[0007]
[Means for Solving the Problems]
The method for producing a silver-toned artificial leather according to the present invention comprises, on a fibrous base material previously treated with amino-modified silicone, a polymer elastic emulsion and a heat-expandable capsule having a shell wall softening point temperature of 80 ° C or higher. Applying the impregnating liquid containing from the surface side, pre-drying at a temperature lower than the shell wall softening point temperature is repeated a plurality of times, then foaming the thermally expandable capsule at a temperature equal to or higher than the shell wall softening point, and simultaneously impregnating the impregnating liquid. It is characterized in that it is dried and subsequently a coat layer made of a polymer elastic material is applied on the surface side.
[0008]
Further, it is preferable that the fibrous base material is made of ultrafine fibers of 0.5 dtex or less, and the diameter of the thermally expandable capsule is 5 to 50 μm.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
In the production method of the present invention, first, an impregnating liquid containing a polymer elastic emulsion and a heat-expandable capsule is applied on a fibrous base material from the surface side.
[0010]
The fiber constituting the fibrous base material may be a fiber having a normal thickness, but is preferably an ultrafine fiber from the viewpoint of a feeling. The fineness of the ultrafine fibers is preferably 0.5 dtex or less, and more preferably 0.001 to 0.3 dtex. Further, as such a fiber used for preparing a fibrous base material, a fiber which finally becomes an ultrafine fiber as described above is preferable, and as such a fiber before ultrafineness, a sea-island type mixed spinning is used. Any of fibers, conjugate spun fibers, and the like can be applied, but it is particularly preferable that the fibers are peelable split type conjugate fibers.
[0011]
As such a fiber used in the present invention, one of conventionally known synthetic resins capable of forming a fiber, such as polyester, polyamide, polyacryl, and polyolefin, or a synthetic fiber composed of two or more resins can be used. Among them, it is particularly preferable to use polyester, polyamide or polyester / polyamide. Polyester to be a fiber includes polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and the like, and polyamide includes nylon-6, nylon-66, nylon-12, and the like. Among them, polyethylene terephthalate, nylon-6 and the like are preferable from the viewpoint of process stability and cost.
[0012]
Further, in the present invention, it is preferable that a sheet is formed from the fibers before the ultra-fine-thinning, and the fibrous base material is subjected to the ultra-thinning treatment. Further, at this time, it is preferable that heat-shrinkable fibers are contained in the fibers before ultra-fine formation that constitute the sheet. By shrinking the fibers by heat after forming the sheet shape, the density of the fibers can be increased before impregnation of the elastic polymer, and the texture is improved. Such a heat-shrinkable fiber is particularly preferably a high-shrinkage polyester fiber having a large shrinkage stress. For example, a heat-shrinkable fiber obtained by spinning a fiber-forming polymer containing polyethylene terephthalate as a main component and then stretching the fiber in low-temperature at a low magnification. Further, it is preferable that the heat-shrinkable fibers exhibit shrinkage characteristics at 50 ° C. or more and 100 ° C. or less by controlling the drawing conditions and the like. Those exhibiting characteristics at a temperature lower than 50 ° C. cause a variation in quality, and those exhibiting characteristics at a temperature higher than 100 ° C. require a large amount of heat and deteriorate productivity. After being formed into a sheet, the shrinkage rate until it becomes a fibrous base material is preferably 5 to 50%, particularly preferably 20 to 40%.
[0013]
Also, most preferably, the fibers constituting the sheet are heat-shrinkable fibers and are composite fibers that can be further divided into two or more types of single fibers. When the heat shrinkage of each single fiber generated by dividing the conjugate fiber is different from each other, division of the conjugate fiber further proceeds during the shrinkage treatment, and a more dense and homogeneous structure can be obtained. For example, it is preferable to use a split-split conjugate fiber that is finally split into ultra-high heat shrinkable polyester fibers and low heat shrinkable polyamide fibers and converted into ultrafine fibers.
[0014]
The sheet made of these fibers is most preferably a nonwoven fabric from the viewpoint of the texture. As a method of forming such a nonwoven fabric, a conventionally known method such as a method of carding from short fibers and entanglement, or a method of forming long fibers into a direct sheet and entanglement can be adopted. In order to obtain a denser and more uniform fibrous base material, it is preferable to use a peelable splittable conjugate fiber which is turned into an ultrafine fiber and entangle with a high-pressure water flow.
[0015]
In the method for producing artificial leather with silver tone according to the present invention, it is necessary that the fibrous base material is previously treated with amino-modified silicone. Generally, an amino-modified silicone is applied and dried. In the present invention, the amino-modified silicone acts between the fibers before the impregnation of the polymer elastic body, whereby the adhesion between the fiber and the polymer elastic body is prevented, and a more flexible structure is obtained.
[0016]
In the production method of the present invention, the preferred amount of the amino-modified silicone component to be attached is 0.1 to 2% by weight, more preferably 0.5 to 1% by weight, based on the weight of the fibrous base material. As a treatment method, it can be obtained by impregnating a fibrous base material with a solution prepared by diluting with water to a concentration of 0.1 to 1% by weight, controlling the amount of squeezing with a nip roll, and then drying. The drying method may be hot-air drying, but by bringing it into contact with a heating roll and drying, it is possible to simultaneously obtain surface smoothness. Further, in the present invention, since the treatment is performed before impregnation of the resin, a high effect is obtained despite such a small amount of adhesion, and the falling off from the finally obtained leather-like sheet is very small. .
[0017]
In the production method of the present invention, an impregnating liquid containing a polymer elastic emulsion and a heat-expandable capsule having a shell wall softening point temperature of 80 ° C. or higher is applied to the fibrous base material thus treated from the surface side. .
As the polymer elastic emulsion used in the present invention, any emulsion may be used as long as it exhibits an elastomeric property after removal of water. Among them, a polyurethane emulsion is preferable in terms of flexibility, strength, weather resistance and the like.
[0018]
Further, in the present invention, it is preferable that the elastic polymer emulsion has heat-sensitive coagulation properties. It is preferable that the temperature at which the coagulation property of the polymer elastic material emulsion develops is at or below the expansion start temperature of the thermally expandable capsule. The temperature at which the coagulation property of the polymer elastic emulsion is exhibited is the temperature at which the emulsion loses fluidity and solidifies when the temperature of the emulsion containing various additives is increased while stirring.
[0019]
Examples of the heat-expandable capsule used in the present invention include those in which a thermoplastic resin is used as a shell and an organic compound having a specific boiling point is encapsulated and encapsulated as a swelling agent. For example, there may be mentioned those obtained by encapsulating and encapsulating isobutane using a vinylidene chloride-acrylonitrile copolymer as a shell. The diameter is preferably 5 to 50 μm. The heat-expandable capsule of the present invention is one in which the shell is softened by heating, and the contained organic compound becomes gas and expands. The expansion start temperature and the maximum expansion point can be changed depending on the type of thermoplastic resin, shell thickness, capsule diameter, and the like.
Further, as the impregnating liquid to be treated, the solid component weight of the thermally expandable capsule is preferably 2 to 10% by weight based on the solid component weight of the elastic polymer.
[0020]
Furthermore, for the purpose of improving various durability such as light resistance, heat resistance, water resistance and solvent resistance of the emulsion, antioxidants, ultraviolet absorbers, stabilizers such as hydrolysis inhibitors, epoxy resins, melamine resins, A crosslinking agent such as an isocyanate compound, an aziridine compound, and a polycarbodiimide compound may be blended and used. Further, various water-soluble or water-dispersible inorganic and organic pigments can be blended for coloring.
[0021]
The method of impregnating the fibrous base material with the impregnating liquid of the present invention is a method of applying from the surface side, and a gravure coating method is preferably used. The number of times of application may be two or more times, but from an industrial point of view, at most 10 times is sufficient, and generally 5 times or less. The amount of adhesion (solid content) in one application is preferably 5 to 15% by weight of the fiber weight after drying, and the total application amount is preferably 50% by weight or less. When the coating is performed a plurality of times as described above, it is preferable that the amount of adhesion per application be 15% by weight or less and the amount of adhesion be reduced as the number of times of application increases. By performing the application in several times in this manner, an impregnated layer composed of a polymer elastic body and fibers is formed on the surface side, and the thermally expandable capsule can be unevenly distributed on the outermost surface side. This is because the voids on the surface of the fibrous base material are reduced by the first application, and only the elastic polymer enters into the interior by the second application, and the thermally expandable capsule having a relatively large diameter remains on the surface.
[0022]
For more stable application, it is preferable to perform additional preliminary drying during application to evaporate unnecessary moisture. For example, a plurality of times, application, after pre-drying is repeated, further additional pre-drying is performed, and then, a plurality of further application, pre-drying is repeated, so that the pre-drying time is shortened to about 5 to 60 seconds. Can be suppressed. At this time, the additional preliminary drying is preferably performed for a long time of about 2 to 30 minutes.
[0023]
The adhesion amount of the elastic polymer at the impregnation stage is preferably 3 to 50% by weight based on 100 parts by weight of the fibrous base material. If the amount (solid content) of the elastic polymer attached is small, the sense of fulfillment of the obtained sheet is reduced, and if it is large, the sheet tends to be hard.
[0024]
In the present invention, it is necessary to further apply the impregnating liquid from the surface after the application pre-drying step of applying the impregnating liquid from the surface and pre-drying at a temperature lower than the shell wall softening point temperature. In order to stabilize the amount of application, it is preferable to apply a small amount in two or three times as described above.
[0025]
When the elastic polymer used has heat-sensitive coagulability, the temperature for the preliminary drying is preferably equal to or higher than the heat-sensitive coagulation temperature. By performing such preliminary drying, excessive permeation of the polymer elastic body due to migration can be prevented.Moreover, since the polymer elastic body is applied in a plurality of times, the foam is unevenly distributed on the surface, and inside the foam, Almost no.
After the impregnating liquid is applied again in this manner, the thermally expandable capsule is foamed at a temperature equal to or higher than the shell wall softening point, and the impregnating liquid is dried.
[0026]
In the present invention, it is necessary to further provide a coating layer made of the elastic polymer on the surface side on which the elastic polymer is applied and dried. The elastic polymer used at this time is not particularly limited, but is most preferably a polyurethane resin from the viewpoint of the feeling.
[0027]
In this case, a small amount may contain a heat-expandable capsule, but it is preferable not to include it in order to obtain smoothness. Further, as a coating method, a conventionally known method can be used, but it is preferable that the coating method be a lamination method that easily satisfies the surface smoothness and pattern. For example, there is a method in which a film layer of a polymer elastic material is formed on release paper, a binder layer of the polymer elastic material is applied, and the resultant is bonded to an impregnated base material. When using an aqueous laminating method, it is preferable to nip with a hot cylinder.
[0028]
In this way, the artificial leather with silver obtained by the production method of the present invention has suitable voids because there are voids in the polymer elastic body, and it is small inside the base material and large in the portion immediately below the coat layer. It has a good texture, good graininess and excellent texture, and is a silver-finished artificial leather suitable for use as a natural leather substitute for shoes and clothing.
[0029]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified.
[0030]
In the examples, “graininess” and “texture” are evaluated in the order of goodness, ○, Δ, and ×, and “wrinkles” are determined based on the presence or absence of wrinkles when folded, and wrinkles are generated. No wrinkles were evaluated as ○, small wrinkles were evaluated as Δ, and large wrinkles were evaluated as x. The “impregnated polyurethane application amount” is a numerical value (%) obtained by visually observing the cross section and dividing the permeation distance of the polymer elastic body from the surface by the total thickness of the cross section for each gravure roll application. ), And “R / F” was determined as the ratio (%) of the polymer elastic body / fiber of the entire fiber composite sheet without dividing the unimpregnated portion and the impregnated portion.
[0031]
[Example 1]
(Preparation of fibrous base material)
Polyethylene terephthalate having shrinkage characteristics as the first component and peelable splittable conjugate fiber having a parent yarn fineness of 4.4 dtex having a 16-split gear type cross section using nylon-6 as the second component are subjected to needle punching and high pressure water entanglement treatment. The entanglement and splitting of the fibers are performed to form a nonwoven fabric having a thickness of 1.05 mm and a basis weight of 241 g / m 2. Then, the nonwoven fabric after the splitting process is immersed in a hot water bath at 75 ° C. for 20 seconds to obtain a first component. The polyethylene terephthalate fiber was shrunk, and the entire area was shrunk by 21% to obtain a nonwoven fabric as a fibrous base material.
[0032]
(Silicone treatment)
Wet pickup of Polon MF-14 (amino-modified silicone softener, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 15% by weight) / water = 2/98 (parts by weight) on the nonwoven fabric obtained in Reference Example 1, The fabric was softened at 200% by weight and dried at 120 ° C. for 5 minutes to obtain a nonwoven fabric.
[0033]
(Preparation of impregnation liquid)
V-2114 (aqueous polyurethane resin, manufactured by Dainippon Ink and Chemicals, Inc., solid content concentration: 40% by weight) / DISPERSE HG-950 (water-dispersible black pigment, manufactured by Dainippon Ink and Chemicals, Inc.) / Hydran WL Assister T2 (urethane-based thickener, manufactured by Dainippon Ink and Chemicals, Inc.) / F-90N (water repellent, manufactured by Meisei Chemical Co., Ltd.) / SD-8i (hydrophobic agent, Dainippon Ink and Chemicals, Inc.) Matsumoto Microsphere-F-50 (thermally expandable microcapsule containing low boiling point hydrocarbon, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) / Water = 70/1/1/1/1/26 (parts by weight) ) To prepare an impregnating liquid (720 mPa · s, 20 ° C.) for gravure coating.
[0034]
(Preparation of fiber composite sheet)
The process of applying the gravure roll (# 110) to the silicone-treated shrink nonwoven fabric and pre-drying (110 ° C., 20 seconds) was repeated for four rolls. In addition, preliminary drying at 90 ° C. for 10 minutes was added to the intermediate step after coating for two rolls. After applying all four rolls and pre-drying, foaming and drying were performed at 130 ° C. for 5 minutes to obtain a fiber composite sheet.
[0035]
When the cross section and the surface state were observed with an electron microscope, the foaming agent was present only in the surface layer, the size was 100 μm or less, and the foaming agent and fibers were observed on the surface.
[0036]
(Creating a coat layer)
Hydran WLS211 (aqueous polyurethane resin, manufactured by Dainippon Ink and Chemicals, Inc., solid content concentration 35% by weight) / DISPERSE HG (water dispersible black pigment, manufactured by Dainippon Ink and Chemicals, Inc.) / Hydran WL Assister T1 (Urethane thickener, manufactured by Dainippon Ink and Chemicals, Inc.) / Hydran WL Assister C2 (isocyanate-based crosslinking agent, manufactured by Dainippon Ink and Chemicals, Inc.) / Hydran WL Assister W1 (leveling agent, Dainippon Ink.) Chemical Industry Co., Ltd.) / Hydran Assister D1 (antifoaming agent, manufactured by Dainippon Ink and Chemicals, Inc.) = 100/5 / 0.25 / 4 / 0.2 / 5 (parts by weight) The coating solution for layer was applied on release paper (AR-144SM, thickness 0.25 mm, manufactured by Asahi Roll Co., Ltd.) at an application thickness of 100 μm (wet). 2 min at 0 ° C., then subjected to drying in two stages for four minutes at 110 ° C., to form a polyurethane resin film (hereinafter referred to as the film layer).
[0037]
Hydran WLA311 (water-based polyurethane resin, manufactured by Dainippon Ink and Chemicals, Inc., solid content concentration: 45% by weight) / DISPERSE HG (water-dispersible black pigment, manufactured by Dainippon Ink and Chemicals, Inc.) / Hydran WL Assister T1 (urethane thickener, manufactured by Dainippon Ink and Chemicals, Inc.) / Hydran WL Assister C2 (isocyanate crosslinker, manufactured by Dainippon Ink and Chemicals, Inc.) = 100/5/0. The adhesive compounding liquid compounded in 1/10 (parts) was applied with a coating thickness of 150 μm (wet) to form a laminate layer. When the water content of the coating solution on the release paper was measured, it was 45.8%.
[0038]
(Preparation of artificial leather with silver tone 1)
The above-mentioned coat layer is immediately bonded to the fiber composite sheet 1, brought into contact with a heating cylinder (surface temperature: 130 ° C.), preheated for 15 seconds, and then heated using the heating cylinder under the condition of a clearance of 1.0 mm. Nipping and further curing at 120 ° C. for 2 minutes were performed. The moisture content of the substrate after curing was 4.1%. Further, aging was performed at 50 ° C. for 24 hours, and the release paper was peeled off to obtain artificial leather 1 with silver tone.
Table 1 shows the physical properties and the like.
[0039]
[Example 2]
Silver in the same manner as in Example 1 except that the silicone treatment in Example 1 was changed to Polon MF-14 (amino-modified silicone softener, manufactured by Shin-Etsu Chemical Co., Ltd.) / Water = 3/97 (parts by weight). A tuned artificial leather was created.
[0040]
When the cross section and surface state of the fiber composite sheet before applying the coat layer were observed with an electron microscope, the foaming agent was present only in the surface layer, the size was 100 μm or less, and the foaming agent and fibers were observed on the surface.
The physical properties and the like are also shown in Table 1.
[0041]
[Example 3]
Silver in the same manner as in Example 1 except that the silicone treatment in Example 1 was changed to PORON MF-14 (amino-modified silicone softener, manufactured by Shin-Etsu Chemical Co., Ltd.) / Water = 4/96 (parts by weight). A tuned artificial leather was created.
[0042]
When the cross section and surface state of the fiber composite sheet before applying the coat layer were observed with an electron microscope, the foaming agent was present only in the surface layer, the size was 100 μm or less, and the foaming agent and fibers were observed on the surface.
The physical properties and the like are also shown in Table 1.
[0043]
[Comparative Example 1]
A silver-finished artificial leather was prepared in the same manner as in Example 1 except that the silicone treatment of Example 1 was not performed.
[0044]
When observing the cross section and surface state of the fiber composite sheet before applying the coat layer with an electron microscope, the foaming agent is present only in the surface layer portion, the size is 100 μm or less, and although the foaming agent and the fiber are observed on the surface, The texture was inferior.
The physical properties and the like are also shown in Table 1.
[0045]
[Comparative Example 2]
Except that the pre-drying of Example 1 was not performed, a silver-finished artificial leather was prepared in the same manner as in Example 1.
[0046]
The impregnated polyurethane penetrated to the inside and became a corrugated cardboard structure when dried. The physical properties and the like are also shown in Table 1.
[0047]
[Comparative Example 3]
Instead of the gravure coating of Example 1, the fibrous base material is immersed in the impregnating liquid, and the fiber composite sheet having an R / F of 35% is formed by nip. Thereafter, the coating layer is formed in the same manner as in Example 1. Granted.
[0048]
The impregnated polyurethane and the foaming agent penetrated to the inside and had a poor texture. The physical properties and the like are also shown in Table 1.
[0049]
[Table 1]
[0050]
【The invention's effect】
The production method of the present invention is a method for producing silver-finished artificial leather which is excellent in good grain feeling and feeling and is preferably used as a natural leather substitute for shoes and clothing.
Claims (5)
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011069019A (en) * | 2009-09-25 | 2011-04-07 | Kuraray Co Ltd | Method for producing grained leather-like sheet |
WO2011114956A1 (en) | 2010-03-16 | 2011-09-22 | 東レ株式会社 | Sheet-like material and method for producing same |
WO2013168653A1 (en) | 2012-05-11 | 2013-11-14 | 東レ株式会社 | Sheet-form product and method for producing same |
KR101727147B1 (en) * | 2015-11-10 | 2017-04-14 | 주식회사 덕성 | Double firing eco friendly synthetic leather and a method of manufacturing the same |
US11326038B2 (en) | 2015-12-09 | 2022-05-10 | Rohm And Haas Company | Crushed foam coating |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107201664B (en) * | 2017-05-24 | 2019-08-30 | 东莞易昌塑胶布业有限公司 | A kind of production method of the lining cloth of adjustable temperature |
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2003
- 2003-05-13 JP JP2003134186A patent/JP4255746B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011069019A (en) * | 2009-09-25 | 2011-04-07 | Kuraray Co Ltd | Method for producing grained leather-like sheet |
WO2011114956A1 (en) | 2010-03-16 | 2011-09-22 | 東レ株式会社 | Sheet-like material and method for producing same |
KR20130006446A (en) | 2010-03-16 | 2013-01-16 | 도레이 카부시키가이샤 | Sheet-like material and method for producing same |
US9932705B2 (en) | 2010-03-16 | 2018-04-03 | Toray Industries, Inc. | Sheet-like material and method for producing same |
WO2013168653A1 (en) | 2012-05-11 | 2013-11-14 | 東レ株式会社 | Sheet-form product and method for producing same |
KR101727147B1 (en) * | 2015-11-10 | 2017-04-14 | 주식회사 덕성 | Double firing eco friendly synthetic leather and a method of manufacturing the same |
US11326038B2 (en) | 2015-12-09 | 2022-05-10 | Rohm And Haas Company | Crushed foam coating |
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