JP4093777B2 - Suede-like artificial leather - Google Patents
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Description
【0001】
【発明の属する技術分野】
本発明は、優れた摩耗性能を有すスエード調人工皮革に関し、より詳しくは、家具、カーシートで特に張り替えの効かないようなハードな用途分野に使用され、マーチンデニール磨耗が30000回以上の高い耐磨耗強度を有し、且つ、中濃色において、磨耗による白化に伴う色落ちの少ない優れた磨耗性を有するスエード調人工皮革に関するものである。
【0002】
【従来の技術】
スエード調人工皮革は、豪華な表面品位やイージーケア性から市場拡大が続いているが、最近では劇場や映画館、ホテルといった公共施設(以下「コントラクト」という)用家具やカーシートといったハードな用途分野、特に耐摩耗性が要求される分野へも積極的に市場開拓している。
スエード調人工皮革を構成する0.4dtex以下の極細繊維の工業的製造方法としては、2種のポリマー成分からなる鞘芯型複合繊維を製造し、その後に一方の成分を化学的に溶解除去する海島繊維法(例えば、特公昭43−14184号公報、特公昭44−18369号公報等)、2種のポリマー成分からなる分割型複合繊維を製造し、2成分の界面を化学的又は物理的手段で分割する割繊繊維法(例えば、特公昭47−49766号公報等)等が知られている。
【0003】
この他に、複合繊維を経由することなく、ポリエチレンテレフタレートからなる単独のポリエステルを溶融紡糸し、それに続く延伸によって製造される直接紡糸法が特公昭63−526号公報や特公昭62−35481号公報に開示されている。この直接紡糸法によって得られる極細繊維は上記、海島繊維法や割繊繊維法による製法に比較して、有機溶媒や溶剤を用いない方法として人体や環境へのリスクが小さいことから規制の厳しい欧州市場では、非常に好感を持って受け入れられている技術である。
この直接紡糸法から製造した極細繊維は数ミリメートルの長さにカットし短繊維として水分散させ抄造法で直接的に均一な不織布シートを製造することが出来るという最大の特徴を有している。
中間層にスクリムと呼ばれる編物、織物を挿入した積層体として一気にシート化することも容易である。
【0004】
更に、柱状流と呼ばれる水流交絡で3次元交絡させると極細繊維同志の他スクリムとの一体交絡が実現出来、その強固な交絡形態により低バインダーにも関わらず高強度、高寸法安定性といった高度な実用性能が保持出来、しかも、低バインダー故にソフト風合いが達成されるなど数々の利点を有した人工皮革を製造することが出来る。
しかし、この直接紡糸法により単糸繊度0.4dtex以下の極細繊維を工業的に製造する為には、使用するポリエチレンテレフタレートの重合度を極限粘度で約0.50dl/g以下と極めて低くする必要があった。
【0005】
このような低重合度原糸を用いて、上記、抄造柱状流交絡させ水性ウレタンを含浸してなるスエード調人工皮革をマーチンデール摩耗処理すると極細繊維がフィブリル化し摩耗面の色相が白っぽく変化(以下「白化」という)し、摩耗処理前の色相と異なってしまうという問題があった。
この現象は、特に、明度(L*)(実施例で測定方法を示す)が30以下の中濃色のスエード調人工皮革において顕著な現象である。
コントラクト用家具やカーシートといった簡単に張り替えの出来ないハードな使用が要求される分野においては、摩耗による白化現象が改善された優れた耐摩耗特性を有すスエード調人工皮革の出現が切望されている。
【0006】
【発明が解決しようとする課題】
本発明は、水系ポリウレタンを含浸してなるスエード調人工皮革において、マーチンデール摩耗で代表される摩耗による白化現象が改善された優れた耐摩耗特性を有すスエード調人工皮革を提供することが目的である。
【0007】
【課題を解決するための手段】
本発明者らは、前述の課題を解決するために極細繊維のフィブリル化現象を詳細に解析し、極細繊維の極限粘度と結晶配向度と耐磨耗性との関係をに着目するに至り、その知見を活かすことで本発明に到達した。
即ち、本発明は、表面層が少なくとも極細単繊維から構成され、水系ポリウレタンが含浸されて染色されたスエード調人工皮革において、マーチンデール摩耗が30000回以上であり、マーチンデール摩耗10000回での摩耗前後の明度差(dL*1)が5.0以下であり、マーチンデール摩耗30000回での摩耗前後の明度差(dL*3)と前記マーチンデール摩耗10000回での摩耗前後の明度差(dL*1)の差が6.0以下であることを特徴とするスエード調人工皮革である。
【0008】
さらに、前記極細単繊維が直接紡糸された繊度0.4dtex以下、極限粘度が0.55dl/g以上、且つ、結晶配向度が80〜90%のポリエステル繊維を表面繊維層として40wt%以上となるようにカットして水分散させ抄造柱状流交絡からなる不織布を基材としてなるスエード調人工皮革を提供することである。
従来より、スエード調人工皮革の家庭用一般家具の分野でのマーチンデール摩耗は、中間層に編織物からなるスクリムを使った人工皮革の場合は、直径2mm以上の面積でスクリムが2カ所を越えて露出した回数をエンドポイントとし、12kPaで20000回以上の性能があれば実用上問題はなく、むしろ、油性や水性の汚れが付きにくい、付いても落としやすいとか制電効果によって冬場の静電気が起こりにくいとか、更に耐光堅牢度や湿摩擦堅牢度など各種堅牢度に優れていることで使い勝手の良さが高く評価され色相の変化は問題にはならなかった。
【0009】
ところが、家具でもホテルや劇場などのコントラクトやカーシートといったハードな分野では、長年に渡ってスエード調の人工皮革の高級な品質を保つ必要があり、白化現象は生地のくたびれ感を消費者に与えることになり印象が悪い。要求される摩耗のエンドポイントは一般家庭用家具以上であり、且つ、改善された白化性能の改善が必須項目になってくる。
本発明者らは、人工皮革の白化の進行を電子顕微鏡観察で克明に解析して、その主因が極細繊維のフィブリル化にあり、フィブリル化されて表面積が増大することで、表面の乱反射が増大し、より白化するというメカニズムを掴んだ。
そして、この白化の程度をCIE(国際照明委員会)推奨の表色系の明度(L*)と、摩耗前後の明度差(dL*)を用いて、白化現象を定量化した。
【0010】
尚、
マーチンデール磨耗10000回の摩耗前後の明度差(dL*1)、
マーチンデール磨耗20000回の摩耗前後の明度差(dL*2)、
マーチンデール磨耗30000回の摩耗前後の明度差(dL*3)、
で示す。
本発明者らは、長年培った欧州家具市場やカーメーカーとのコンタクトによる情報を基に、水性ウレタンからなるスエード調人工皮革のコントラクトやカーシート分野でのマーチンデール摩耗の耐磨耗回数(エンドポイント)は最低30000回が要求される。
【0011】
従来の、ポリエステル繊維の極限粘度が0.50dl/g以下の低粘度糸使いの一例として、極限粘度0.50dl/g、結晶配向度90%の極細糸からなる人工皮革での明度(L*)とマーチンデール摩耗前後の明度差(dL*)の関係をとると第1図に示すように淡色域から濃色域にかけて曲線的に明度差(dL*)が変化し、マーチンデール摩耗30000回で明度(L*)30の中色域では、明度差(dL*3)が12.0以上になり極端に白化するという問題があった。
本発明の設計によれば、マーチンデール摩耗30000回で明度(L*)30の中色域でも、明度差(dL*3)は9.0以下に抑えることが出来、白化現象を大幅に小さくすることができた。
【0012】
本発明のスエード調人工皮革においては、マーチンデール摩耗が30000回以上であることが必要である。より好ましくは、マーチンデール摩耗が35000回以上であり、特に好ましくは40000回以上である。
本発明においては、マーチンデール摩耗10000回での摩耗前後の明度差(dL*1)は、5.0以下であることが必要である。より好ましくは、明度差(dL*1)は、4.0以下である。
本発明においては、マーチンデール摩耗30000回での摩耗前後の明度差(dL*3)と前記マーチンデール摩耗10000回での摩耗前後の明度差(dL*1)との差が6.0以下であることが必要である。より好ましくは、5.0以下である。
【0013】
本発明におけるポリエステル極細繊維において、その極限粘度は、マーチンデール摩耗の摩耗減量と相関が強く、耐磨耗回数(エンドポイント)に大きく影響する。磨耗荷重12kPaでのマーチンデール磨耗回数が30000回以上であり、上記の2つの明度差特性を達成する上で、ポリエステル極細繊維の極限粘度が0.55dl/g以上が好ましく、より好ましくは0.58dl/g以上である。
本発明のポリエステル極細繊維において、その結晶配向度は、極細繊維のフィブリル化現象に大きな影響を与え、X線回折法(実施例で記載している)による測定では、極細繊維のフィブリル化現象による白化を抑制する為に、極細繊維の結晶配向度が80〜90%のものが好ましく、より好ましくは、82〜88%である。
【0014】
結晶配向度が80%に満たないものは、ポリエステル極細繊維の残留伸度が100%以上もある未延伸糸の領域の繊維であり、繊維の微細構造としては結晶性が不完全であり、マーチンデール摩耗の耐磨耗性が低下し易い。
結晶配向度が90%を越えると、糸としては強靱な構造を呈することになり、マーチンデール摩耗による摩耗減量は著しく抑制されエンドポイントは飛躍的に向上するが、フィブリル化現象は反対に加速され、白化に対しては有効性が期待出来ない。この領域の残留伸度は20〜30%付近である。
本発明の結晶配向度80〜90%の原糸は、残留伸度50〜70%程度のものに該当する。
本発明の結晶配向度80〜90%の原糸を実現する方法としては、延伸倍率を下げるか、あるいは、溶融紡糸の紡糸速度を2000〜5000m/minで紡出した半延伸糸を用いることなどが挙げられる。
【0015】
マーチンデール摩耗の耐磨耗性を向上させる方策としては、上記原糸特性を有することが好ましい。
一般に耐磨耗性を向上させる方策として、人工皮革生地の目付量を増やすことも考えられるが、原糸の使用量増加によるコストアップにつながり、さらにスクリムを用いる場合にはスクリムと極細糸との交絡性の低下を招くなど新たな別の問題が発生することになり、非効率的であるといえる。
本発明に用いる極細繊維としては、原糸繊度として、0.40dtex以下が好ましい。表面の高級感の観点からすると、さらに好ましくは、0.25dtex以下である。
本発明では、上記極細繊維を少なくとも表層に40wt%以上含有させることが好ましく、更に好ましくは、50wt%以上である。
【0016】
抄造法を用いれば、極細繊維の均一分散が容易である為、効率の良い効果を発揮させることが出来る。耐光性を高める為には、少し太めの原糸を混ぜることもできるし、その他の要求特性に応じて、適宜、繊維の種類、繊度、形状、及び混合比率を変更することは十分可能である。
本発明は、抄造、柱状流交絡からなる中間層にスクリムと呼ばれる織編物を挿入した湿式不織布を基材としたものであることが好ましい。スクリムがないと強度が不十分で実用性に乏しい。
ニードルパンチからなる乾式不織布においては、極細繊維から直接的にシートを形成する場合、均一性の保持に難があり、更に繊維交絡点が少なく、緻密な起毛発現がむつかしく、その為に、バインダーであるポリウレタンを多量に含浸させて実用性能を持たせる必要があり、風合いが犠牲になることが多い。
【0017】
本発明で用いることができる、スクリム法からなる湿式不織布における特徴としては、少量のバインダー付与で、効率の良い実用性能が発揮出来る点であり、その為に、ソフトな風合い、十分な強度、良好な寸法安定性などの性能向上が期待できる。
スクリムとしては、共重合体を含めたポリエステルが望ましいが、特に素材は限定しない。構成原糸としては、55〜165dtexの汎用糸で織物であれば撚糸、加工糸として織密度50〜60本/inchで経、緯設計したもの、編物であれば、24〜28ゲージ程度の丸編みなどが好適である。
【0018】
本発明の重要な点は、水系ポリウレタンを用いたスエード調人工皮革であることである。本発明者らは既に、特許登録第3047951号で無機塩による感熱凝固法を実用化しているが、水系ポリウレタンは、スエードを有する起毛の根本付近において、バインダー効果が強いことが特徴であり、マーチンデール摩耗での耐磨耗性向上効果が得られ易く、その為に原糸の磨耗性特性が溶剤系ポリウレタンに比較して、水系ポリウレタンの方が現れ易いという特徴を有する。
本発明の適用は、上記感熱凝固法のみに限定するものではなく、水系ポリウレタンの極細繊維とのバインダー作用の強さから、染色後に裏面からのバックコート法のような方法で極少量の水系ポリウレタンを付着させる方法などにも適用出来る。
【0019】
溶剤系のポリウレタンの場合は、その含有率が30〜40wt%であるのに対し、本発明の水系ポリウレタンの場合は、上記理由により、含有率が15wt%以下が好ましく、更に好ましくは、6〜12wt%である。6wt%未満であれば、マーチンデール摩耗のエンドポイントが極端に小さくなる。
水系ポリウレタンとしては、エーテル系、エステル系、ポリカーボネート系など広く適用出来る。
又、ポリウレタン中に耐光向上剤、耐熱安定剤、難燃剤等の添加剤を用いたものも何ら問題ない。
【0020】
【発明の実施の形態】
以下に実施例などにより本発明を具体的に説明するが、本発明は実施例などにより何ら限定されるものではない。
なお、本発明における物性の測定方法及び測定条件は以下の通りである。
(1)極限粘度
極限粘度[η](dl/g)は次式の定義に基づいて求められる値である。
[η]=Lim(ηr−1)/C
C→0
式中のηrは、純度98%以上のo−クロロフェノール溶媒で溶解したポリマーの希釈溶液の35℃での粘度を同一温度で測定した上記溶媒の粘度で除した値であり、相対粘度と定義されているものである。Cは、g/100mlで表されるポリマー濃度である。
【0021】
(2)結晶配向度
X線回折装置を用い、試料の厚みを約0.5mmとして、以下の条件で回折角2θが7度から35度までの回折強度曲線を描く。
測定条件は、30kV、80A、スキャンニング速度1度/分、チャート速度10mm/分、タイムコンスタント1秒、レシーピングスリット0.3mmとする。
2θ=16度及び22度に描かれる反射面を各々(010)、(110)とする。更に、(010)面を−180度〜+180度方位角方向に回折強度曲線を描く。
±180度で得られる回折強度曲線の平均値をとり、水平線を引きベースラインとする。ピークの頂点からベースラインに垂線を下ろし、その高さの中点を求める。中点を通る水平線を引き、これと回折強度曲線との2つの交点間の距離を測定し、この値を角度に換算した値を配向角Hとする。
結晶配向度は、次式で与えられる。
結晶配向度(%)=(180−H)×100/180
【0022】
(3)摩耗性
JIS−L−1096 E法(マーチンデール法)押圧荷重12kPaとし、エンドポイントの定義は直径2mm以上の面積でスクリムが2カ所を越えて露出した回数とした。
(4)明度、明度差
ミノルタCM3500Dを用いて明度(L*)を測定し、摩耗前後の明度から明度差(dL*1)、(dL*2)、(dL*3)を絶対値として求めた。
【0023】
【実施例】
以下に実施例を用いて本発明を詳細に説明するが、本発明はそれらに限定されるものではない。
【実施例1〜3、参考例1、比較例1〜4】
直接紡糸法により表−1に示す極限粘度と結晶配向度を有す単繊維繊度0.17dtexのポリエステル繊維を製造し、長さ5mmに切断した後、水中に分散させ表層用と裏層用の抄造スラリーを作成した。表層目付100g/m2 、裏層目付50g/m2 とし、その中間に82dtex/36fのポリエステル繊維からなるガーゼ状の織物をスクリムとして挿入し、三層積層構造の不織布シートを連続抄造で製造した。次いで、高速水流の噴射により三次元交絡不織布を得た。高速水流は孔径0.1mmの直進流噴射ノズルを用いて表層から4.0MPa、裏層から3.0MPaの圧力で噴射して、ピンテンターで乾燥し、目付200g/m2 のシート状物を製造した。このシート状物の表層を#400のサンドペーパーでバフィングし、次いで、9wt%濃度のポリエーテル系の水系ポリウレタンに3wt%の芒硝を添加した液を付着率12wt%となるように含浸し、ピンテンター乾燥機で3分間加熱乾燥し人工皮革原反を作った。
【0024】
この人工皮革原反を130℃、30分液流染色機でブルーの分散染料(BlueFBL住友化学製)で染色し、アルカリで還元洗浄を実施し、明度(L*)26のスエード調人工皮革製品を得た。このものをマーチンデール磨耗により、30000回までの摩耗性を測定し、明度差(dL*1)、(dL*2)、(dL*3)及びエンドポイント(耐磨耗回数)評価した。結果を実施例1〜3、参考例1、比較例1〜4として、表−1にまとめて示した。
実施例1、2、3は、特に白化現象が改善された優れた耐摩耗性能を有していた。
【0025】
【参考例2、実施例4〜9、比較例5、6】
実施例1と同様に、表−2に示す極細糸からなる人工皮革原反を用いて、ベージュ、茶、濃紺に染色し、明度(L*)はそれぞれ60、28、18であった。このものを、参考例2、実施例4〜9、比較例5、6として、表−2に摩耗性能の結果をまとめて示した。
本発明によれば、染色後の明度(L*)が30以上の淡色領域では勿論のこと、明度(L*)30以下の中濃色においても、白化現象が改善された優れた摩耗性能を有していた。
【0026】
【実施例10〜12、比較例7、8】
表層用として直接紡糸法にて極限粘度0.58dl/gで結晶配向度87%からなる0.17dtex糸(a)と極限粘度0.45dl/gで結晶配向度92%からなる0.35dtex糸(b)の混合率を種々変更して目付100g/m2 の抄造不織布シートを作り、裏層は実施例1と同様な設計で三次元交絡不織布とした。
実施例1の条件で加工し、青系の分散染料で染色仕上げを行った。原糸混合比率が異なる為、同浴染色すると微妙に明度は異なるがいずれも明度(L*)30以下で仕上がった。摩耗評価の結果を、表−3にまとめた。
本発明の極細糸を用いて、40wt%以上混合することで優れた摩耗性能が発現する。
【0027】
【表1】
【0028】
【表2】
【0029】
【表3】
【0030】
【発明の効果】
本発明によれば、表面層が少なくとも極細単繊維から構成され、水系ポリウレタンが含浸されて染色されたスエード調人工皮革において、マーチンデール摩耗が30000回以上であり、マーチンデール摩耗による白化現象が改善され、磨耗前後の明度差(dL*1)が非常に小さい、耐磨耗性の良好なスエード調人工皮革を提供できる。
【図面の簡単な説明】
【図1】極限粘度0.50dl/g、結晶配向度90%の極細糸からなる人工皮革で明度(L*)とマーチンデール摩耗前後の明度差(dL*)の関係を示した図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a suede-like artificial leather having excellent wear performance. More specifically, the present invention is used in a hard application field that is not particularly effective for furniture and car seats, and has a high martin denier wear of 30000 times or more. The present invention relates to a suede-like artificial leather having an abrasion resistance strength and having excellent wear resistance with less color fading due to whitening due to abrasion in a medium dark color.
[0002]
[Prior art]
Suede-like artificial leather continues to expand its market due to its luxurious surface quality and easy-care properties, but recently it has been used for hardware such as furniture and car seats for public facilities such as theaters, movie theaters, and hotels (hereinafter referred to as “contracts”). The market is also actively cultivated in fields that require wear resistance.
As an industrial production method for ultrafine fibers of 0.4 dtex or less constituting suede-like artificial leather, a sheath-core type composite fiber composed of two polymer components is produced, and then one component is chemically dissolved and removed. Sea island fiber method (for example, Japanese Patent Publication No. 43-14184, Japanese Patent Publication No. 44-18369, etc.) Manufactures a split type composite fiber composed of two kinds of polymer components, and a chemical or physical means for the interface between the two components. A split fiber method (for example, Japanese Patent Publication No. 47-49766) is known.
[0003]
In addition, a direct spinning method produced by melt-spinning a single polyester made of polyethylene terephthalate without going through a composite fiber and subsequent drawing is disclosed in Japanese Patent Publication Nos. 63-526 and 62-35481. Is disclosed. The ultrafine fiber obtained by this direct spinning method is less strict in Europe because it has less risk to the human body and the environment as a method that does not use an organic solvent or solvent compared to the production method by the sea island fiber method or the split fiber method. It is a technology that is very well accepted in the market.
The ultrafine fibers produced from this direct spinning method have the greatest feature that they can be cut to a length of several millimeters and dispersed in water as short fibers to produce a uniform non-woven fabric sheet directly by papermaking.
It is also easy to form a sheet as a laminate in which a knitted fabric or a fabric called scrim is inserted in the intermediate layer.
[0004]
In addition, when three-dimensional entanglement is made by hydroentanglement called columnar flow, it is possible to realize entanglement with other scrims in combination with ultrafine fibers, and due to its strong entanglement form, high strength and high dimensional stability are achieved despite low binders. It is possible to produce artificial leather having many advantages such as being able to maintain practical performance and achieving a soft texture because of its low binder.
However, in order to industrially produce ultrafine fibers having a single yarn fineness of 0.4 dtex or less by this direct spinning method, the polymerization degree of polyethylene terephthalate to be used needs to be extremely low at an intrinsic viscosity of about 0.50 dl / g or less. was there.
[0005]
Using such a low-polymerization yarn, the above-mentioned suede-like artificial leather impregnated with paper-made column-like entangled water-based urethane is subjected to martindale abrasion treatment, and ultrafine fibers are fibrillated and the hue of the wear surface changes whitish There is a problem that it is different from the hue before the abrasion treatment.
This phenomenon is particularly remarkable in a medium-coloured suede-like artificial leather having a lightness (L *) (measurement method shown in the examples) of 30 or less.
In fields that require hard use that cannot be easily replaced, such as contract furniture and car seats, the emergence of suede-like artificial leather with excellent wear resistance and improved whitening due to wear Yes.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a suede-like artificial leather having excellent wear resistance with improved whitening phenomenon caused by wear represented by martindale wear in a suede-like artificial leather impregnated with water-based polyurethane. It is.
[0007]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have analyzed the fibrillation phenomenon of ultrafine fibers in detail, and have focused on the relationship between the intrinsic viscosity of ultrafine fibers, the degree of crystal orientation, and the wear resistance. The present invention has been achieved by utilizing the knowledge.
That is, according to the present invention, in a suede-like artificial leather whose surface layer is composed of at least an ultrafine single fiber and is dyed by impregnation with water-based polyurethane, the Martindale wear is 30,000 times or more, and the wear of the Martindale wear is 10,000 times. The difference in brightness before and after (dL * 1) is 5.0 or less, the difference in brightness before and after the abrasion at 30,000 Martindale wear (dL * 3) and the difference in brightness before and after the wear at 10,000 dales of Martindale (dL) * 1) A suede-like artificial leather characterized by a difference of 6.0 or less.
[0008]
Further, a polyester fiber having a fineness of 0.4 dtex or less, an intrinsic viscosity of 0.55 dl / g or more, and a crystal orientation of 80 to 90% as a surface fiber layer is 40 wt% or more when the ultrafine single fiber is directly spun. Thus, it is intended to provide a suede-like artificial leather whose base material is a nonwoven fabric made of paper-making columnar flow entanglement that is cut and dispersed in water.
Conventionally, Martindale wear in the field of general household furniture of suede-like artificial leather is more than 2 scrims with an area of 2 mm in diameter or more in the case of artificial leather using scrim made of knitted fabric in the intermediate layer If the performance is more than 20000 times at 12 kPa, there is no problem in practical use. Rather, oily or water-based dirt is difficult to attach, and it is easy to remove even if attached. The ease of use was highly valued because it was difficult to occur, and it was also excellent in various fastnesses such as light fastness and fastness to wet friction, and the change in hue did not become a problem.
[0009]
However, in furniture, such as hotels and theaters such as contracts and car seats, it is necessary to maintain the quality of suede-like artificial leather for many years, and the whitening phenomenon gives consumers a feeling of fabric tucking. The impression is bad. The required end point of wear is more than general household furniture, and improved whitening performance is an essential item.
The present inventors analyzed the progress of whitening of artificial leather with an electron microscope, and the main cause is the fibrillation of ultrafine fibers, and the surface reflection is increased by increasing the surface area by fibrillation. And I grasped the mechanism of more whitening.
The degree of whitening was quantified using the brightness (L *) of the color system recommended by CIE (International Lighting Commission) and the brightness difference (dL *) before and after wear.
[0010]
still,
Martindale wear brightness difference (dL * 1) before and after 10,000 wear
Martindale wear brightness difference (dL * 2) before and after 20000 wear
Brightness difference (dL * 3) before and after 30000 martindale wear
It shows with.
Based on information cultivated over many years in contact with the European furniture market and car manufacturers, the inventors have developed a contract for suede-like artificial leather made of water-based urethane and the number of wear resistances of Martindale wear in the car seat field (end Point) is required at least 30000 times.
[0011]
As an example of conventional use of a low-viscosity yarn having an intrinsic viscosity of polyester fiber of 0.50 dl / g or less, lightness in artificial leather made of ultrafine yarn having an intrinsic viscosity of 0.50 dl / g and a crystal orientation of 90% (L * ) And the brightness difference before and after Martindale wear (dL *), the lightness difference (dL *) changes in a curve from the light color range to the dark color range as shown in FIG. In the middle color gamut of lightness (L *) 30, the lightness difference (dL * 3) is 12.0 or more, which causes a problem of extreme whitening.
According to the design of the present invention, the brightness difference (dL * 3) can be suppressed to 9.0 or less even in the middle color gamut of lightness (L *) 30 with 30000 martindale wear, and the whitening phenomenon is greatly reduced. We were able to.
[0012]
In the suede-like artificial leather of the present invention, the Martindale wear needs to be 30000 times or more. More preferably, the Martindale wear is 35000 times or more, and particularly preferably 40000 times or more.
In the present invention, the difference in brightness (dL * 1) before and after the wear after 10,000 wear of Martindale needs to be 5.0 or less. More preferably, the brightness difference (dL * 1) is 4.0 or less.
In the present invention, the difference between the brightness difference (dL * 3) before and after the abrasion at 30,000 Martindale wear and the brightness difference (dL * 1) before and after the wear at 10000 Martindale wear is 6.0 or less. It is necessary to be. More preferably, it is 5.0 or less.
[0013]
In the polyester ultrafine fiber of the present invention, the intrinsic viscosity has a strong correlation with the wear loss of Martindale wear, and greatly affects the number of wear resistance (end point). When the wear load is 12 kPa, the number of wear of Martindale is 30000 times or more, and in order to achieve the above two lightness difference characteristics, the intrinsic viscosity of the polyester microfiber is preferably 0.55 dl / g or more, more preferably 0.8. It is 58 dl / g or more.
In the polyester ultrafine fiber of the present invention, the degree of crystal orientation has a great influence on the fibrillation phenomenon of the ultrafine fiber, and the measurement by the X-ray diffraction method (described in the examples) is due to the fibrillation phenomenon of the ultrafine fiber. In order to suppress whitening, the ultrafine fiber preferably has a crystal orientation of 80 to 90%, more preferably 82 to 88%.
[0014]
Those having a degree of crystal orientation of less than 80% are fibers in an undrawn yarn region in which the residual elongation of the polyester ultrafine fiber is 100% or more, and the fine structure of the fiber is incompletely crystalline. The wear resistance of Dale wear tends to decrease.
If the degree of crystal orientation exceeds 90%, the yarn will have a tough structure, and the weight loss due to Martindale wear will be remarkably suppressed and the endpoint will be improved dramatically, but the fibrillation phenomenon will be accelerated on the contrary. The effectiveness against whitening cannot be expected. The residual elongation in this region is around 20-30%.
The raw yarn having a crystal orientation of 80 to 90% according to the present invention corresponds to one having a residual elongation of about 50 to 70%.
As a method for realizing the original yarn having a crystal orientation of 80 to 90% according to the present invention, the draw ratio is lowered, or a half-drawn yarn obtained by spinning at a spinning speed of melt spinning of 2000 to 5000 m / min is used. Is mentioned.
[0015]
As a measure for improving the abrasion resistance of Martindale wear, it is preferable to have the above-mentioned raw yarn characteristics.
In general, as a measure to improve the abrasion resistance, it is possible to increase the weight of the artificial leather fabric, but this leads to an increase in the cost due to the increase in the amount of raw yarn used. Another new problem such as a decrease in confounding occurs, which can be said to be inefficient.
The ultrafine fiber used in the present invention preferably has a raw yarn fineness of 0.40 dtex or less. From the viewpoint of high-quality surface, it is more preferably 0.25 dtex or less.
In the present invention, the ultrafine fiber is preferably contained in at least 40 wt% or more in the surface layer, and more preferably 50 wt% or more.
[0016]
If the paper making method is used, it is easy to uniformly disperse the ultrafine fibers, so that an efficient effect can be exhibited. In order to increase the light resistance, it is possible to mix a slightly thicker raw yarn, and it is possible to appropriately change the fiber type, fineness, shape, and mixing ratio according to other required characteristics. .
The present invention is preferably based on a wet nonwoven fabric in which a woven or knitted fabric called scrim is inserted into an intermediate layer made of papermaking and columnar entanglement. Without a scrim, the strength is insufficient and practicality is poor.
In dry nonwoven fabrics consisting of needle punches, when forming a sheet directly from ultrafine fibers, it is difficult to maintain uniformity, and furthermore, there are few fiber entanglement points and it is difficult to develop dense napping. It is necessary to impregnate a certain amount of polyurethane to give practical performance, and the texture is often sacrificed.
[0017]
A feature of the wet nonwoven fabric made of the scrim method that can be used in the present invention is that a small amount of binder can be applied, and an efficient practical performance can be exhibited. Therefore, soft texture, sufficient strength, good It can be expected to improve performance such as dimensional stability.
As the scrim, polyester including a copolymer is desirable, but the material is not particularly limited. Constituent yarns are 55-165 dtex general-purpose yarns that are twisted if they are woven fabrics, warped and weft-designed as processed yarns at a weaving density of 50-60 yarns / inch, and if knitted, rounds of about 24 to 28 gauge Knitting or the like is preferred.
[0018]
The important point of the present invention is that it is a suede-like artificial leather using an aqueous polyurethane. The present inventors have already put into practical use a thermal coagulation method using inorganic salts in Patent Registration No. 3047951, but water-based polyurethane is characterized by a strong binder effect in the vicinity of the root of raised nail having suede. The effect of improving the abrasion resistance due to Dale wear is easily obtained, and for this reason, the wear property of the raw yarn is characterized by the fact that water-based polyurethane is more likely to appear than solvent-based polyurethane.
The application of the present invention is not limited to the heat-sensitive coagulation method described above, but due to the strength of the binder action with the ultrafine fibers of the aqueous polyurethane, a very small amount of aqueous polyurethane can be obtained by a method such as a back coat method from the back after dyeing. It can also be applied to a method of adhering.
[0019]
In the case of solvent-based polyurethane, the content is 30 to 40 wt%, whereas in the case of the aqueous polyurethane of the present invention, the content is preferably 15 wt% or less, more preferably 6 to 6 wt. 12 wt%. If it is less than 6 wt%, the end point of Martindale wear becomes extremely small.
As the water-based polyurethane, ether-based, ester-based, polycarbonate-based and the like can be widely applied.
Also, there is no problem with polyurethane using additives such as light resistance improvers, heat stabilizers, and flame retardants.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
In addition, the measuring method and measuring conditions of the physical property in this invention are as follows.
(1) Intrinsic viscosity Intrinsic viscosity [η] (dl / g) is a value determined based on the definition of the following equation.
[Η] = Lim (ηr−1) / C
C → 0
Ηr in the formula is a value obtained by dividing the viscosity at 35 ° C. of a diluted polymer solution dissolved in an o-chlorophenol solvent having a purity of 98% or more by the viscosity of the solvent measured at the same temperature, and is defined as a relative viscosity. It is what has been. C is the polymer concentration expressed in g / 100 ml.
[0021]
(2) Degree of crystal orientation Using an X-ray diffractometer, draw a diffraction intensity curve with a diffraction angle 2θ of 7 degrees to 35 degrees under the following conditions with a sample thickness of about 0.5 mm.
The measurement conditions are 30 kV, 80 A, scanning speed 1 degree / minute, chart speed 10 mm / minute, time constant 1 second, and receiving slit 0.3 mm.
The reflection surfaces drawn at 2θ = 16 degrees and 22 degrees are (010) and (110), respectively. Further, a diffraction intensity curve is drawn on the (010) plane in the azimuth direction of −180 degrees to +180 degrees.
An average value of diffraction intensity curves obtained at ± 180 degrees is taken, and a horizontal line is drawn as a baseline. A perpendicular line is dropped from the peak apex to the base line, and the midpoint of the height is obtained. A horizontal line passing through the midpoint is drawn, the distance between two intersections of this and the diffraction intensity curve is measured, and the value obtained by converting this value into an angle is defined as an orientation angle H.
The degree of crystal orientation is given by the following equation.
Crystal orientation (%) = (180−H) × 100/180
[0022]
(3) Abrasion JIS-L-1096 E method (Martindale method) The pressing load was 12 kPa, and the definition of the end point was the number of times the scrim was exposed beyond two locations in an area of 2 mm or more in diameter.
(4) Lightness, Lightness Difference Using a Minolta CM3500D, lightness (L *) is measured, and lightness differences (dL * 1), (dL * 2), and (dL * 3) are obtained as absolute values from the lightness before and after wear. It was.
[0023]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Examples 1 to 3, Reference Example 1 and Comparative Examples 1 to 4
A polyester fiber having a single fiber fineness of 0.17 dtex having the intrinsic viscosity and crystal orientation shown in Table 1 by direct spinning is manufactured, cut into a length of 5 mm, and then dispersed in water to be used for the surface layer and the back layer. A papermaking slurry was prepared. A gauze-like woven fabric made of polyester fibers of 82 dtex / 36f was inserted as a scrim between the surface layer basis weight of 100 g / m 2 and the back layer basis weight of 50 g / m 2, and a three-layer laminated nonwoven fabric sheet was produced by continuous papermaking. . Next, a three-dimensional entangled nonwoven fabric was obtained by jetting high-speed water flow. The high-speed water flow is sprayed at a pressure of 4.0 MPa from the surface layer and 3.0 MPa from the back layer using a straight flow jet nozzle having a hole diameter of 0.1 mm, and dried with a pin tenter to produce a sheet-like material having a basis weight of 200 g / m 2. did. The surface layer of this sheet-like material is buffed with # 400 sandpaper, and then impregnated with a 9 wt% polyether-based water-based polyurethane with 3 wt% sodium sulfate added so that the adhesion rate is 12 wt%. Artificial leather raw fabric was made by heating and drying with a dryer for 3 minutes.
[0024]
This artificial leather fabric is dyed with a blue disperse dye (Blue FBL, manufactured by Sumitomo Chemical Co., Ltd.) at 130 ° C for 30 minutes using a liquid dyeing machine, reduced and washed with alkali, and a lightness (L *) 26 suede-like artificial leather product. Got. This product was measured for abrasion by Martindale wear up to 30000 times, and evaluated for lightness difference (dL * 1), (dL * 2), (dL * 3) and end point (number of wear resistance). The results are summarized in Table 1 as Examples 1 to 3, Reference Example 1 and Comparative Examples 1 to 4.
Examples 1, 2, and 3 had excellent wear resistance with particularly improved whitening phenomenon.
[0025]
[ Reference Example 2, Examples 4 to 9 , Comparative Examples 5 and 6]
In the same manner as in Example 1, dyed beige, brown, and dark blue using artificial leather raw fabric made of ultrafine yarn shown in Table 2, and the lightness (L *) was 60, 28, and 18, respectively. The results are shown in Table 2 as Reference Example 2, Examples 4 to 9 , and Comparative Examples 5 and 6, and the results of wear performance are collectively shown in Table-2.
According to the present invention, excellent wear performance with improved whitening phenomenon can be obtained not only in light-colored regions having a lightness (L *) of 30 or more after dyeing, but also in medium-dark colors having a lightness (L *) of 30 or less. Had.
[0026]
Examples 10 to 12 and Comparative Examples 7 and 8
For the surface layer, 0.17 dtex yarn (a) having an intrinsic viscosity of 87% with an intrinsic viscosity of 0.58 dl / g and 0.35 dtex yarn having an intrinsic viscosity of 92% with an intrinsic viscosity of 0.45 dl / g by a direct spinning method. A papermaking nonwoven fabric sheet having a basis weight of 100 g / m 2 was prepared by variously changing the mixing ratio of (b), and the back layer was a three-dimensional entangled nonwoven fabric with the same design as in Example 1.
It was processed under the conditions of Example 1 and dyed and finished with a blue disperse dye. Since the mixing ratio of the raw yarns is different, the brightness is slightly different when dyed in the same bath, but both are finished with a brightness (L *) of 30 or less. The results of wear evaluation are summarized in Table 3.
By using the ultrafine yarn of the present invention and mixing 40 wt% or more, excellent wear performance is exhibited.
[0027]
[Table 1]
[0028]
[Table 2]
[0029]
[Table 3]
[0030]
【The invention's effect】
According to the present invention, in a suede-like artificial leather whose surface layer is composed of at least ultrafine single fibers and dyed by impregnation with water-based polyurethane, the Martindale wear is 30000 times or more, and the whitening phenomenon due to the Martindale wear is improved. In addition, it is possible to provide a suede-like artificial leather having a very small lightness difference (dL * 1) before and after abrasion and excellent wear resistance.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between brightness (L *) and brightness difference (dL *) before and after Martindale wear in an artificial leather made of ultrafine yarn having an intrinsic viscosity of 0.50 dl / g and a crystal orientation of 90%. .
Claims (2)
(1)マーチンデール摩耗が30000回以上である。
(2)マーチンデール摩耗10000回での摩耗前後の明度差(dL*1)が5.0以下 である。
(3)マーチンデール摩耗30000回での摩耗前後の明度差(dL*3)と前記マーチ ンデール摩耗10000回での摩耗前後の明度差(dL*1)との差が6.0以下 である。In a suede-like artificial leather having a surface layer composed of at least ultrafine single fibers and dyed by impregnation with water-based polyurethane, the ultrafine single fibers are directly spun into a fineness of 0.4 dtex or less and have an intrinsic viscosity of 0.55 dl / g. A polyester fiber cut into short fibers having a degree of crystal orientation of 80 to 90%, containing 40 wt% or more as a surface fiber layer, and satisfying the following conditions (1) to (3) Suede-like artificial leather characterized by satisfaction.
(1) Martindale wear is 30000 times or more.
(2) Lightness difference (dL * 1) before and after abrasion at 10,000 dales of Martindale is 5.0 or less.
(3) The difference between the brightness difference (dL * 3) before and after the abrasion at 30,000 Martindale wear and the brightness difference (dL * 1) before and after the wear at 10000 Martindale wear is 6.0 or less.
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JP5101435B2 (en) * | 2008-08-26 | 2012-12-19 | 東レ株式会社 | Dense artificial leather and method for producing the same |
CN104562727A (en) * | 2013-10-27 | 2015-04-29 | 江苏国信合成革有限公司 | Environment-friendly water-based color-changing synthetic leather and preparation method thereof |
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JP6745078B2 (en) * | 2015-12-07 | 2020-08-26 | 株式会社クラレ | Napped artificial leather |
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---|---|---|---|---|
JPS55142756A (en) * | 1979-04-18 | 1980-11-07 | Asahi Chemical Ind | Raised artificial leather with excellent dyeing fastness and production |
JP3047951B2 (en) * | 1993-04-30 | 2000-06-05 | 旭化成工業株式会社 | Manufacturing method of artificial leather with good soft abrasion resistance |
JPH09119063A (en) * | 1995-10-27 | 1997-05-06 | Toray Textile Kk | Staple fiber flock for napping and napped structure |
JPH09157995A (en) * | 1995-12-01 | 1997-06-17 | Toray Textile Kk | Raised fabric |
JP3226024B2 (en) * | 1998-02-02 | 2001-11-05 | 旭化成株式会社 | Brushed artificial leather with high abrasion resistance |
JP3742213B2 (en) * | 1998-02-18 | 2006-02-01 | 株式会社クラレ | Leather-like sheet |
JP3280302B2 (en) * | 1998-03-18 | 2002-05-13 | 旭化成株式会社 | Base cloth and artificial leather for artificial leather |
JP2000290342A (en) * | 1999-04-12 | 2000-10-17 | Toray Ind Inc | Polyurethane and leathery sheety material prepared therefrom |
JP4066556B2 (en) * | 1999-04-12 | 2008-03-26 | 東レ株式会社 | Polyurethane and leather-like sheet using the same |
JP2000303367A (en) * | 1999-04-22 | 2000-10-31 | Toray Ind Inc | Artificial leather having napping |
JP2000303366A (en) * | 1999-04-22 | 2000-10-31 | Toray Ind Inc | Grained artificial leather |
JP4267145B2 (en) * | 1999-10-04 | 2009-05-27 | 株式会社クラレ | Napped fiber sheet and method for producing the same |
-
2002
- 2002-03-14 JP JP2002069582A patent/JP4093777B2/en not_active Expired - Fee Related
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JP2003268680A (en) | 2003-09-25 |
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